TWI260329B - High sensitivity curable resin, curable resin composition, method for producing them, color filter and liquid crystal panel - Google Patents

Abstract

To obtain a high sensitivity curable resin for preventing rise in viscosity of the curable resin or improving transparency, if required. This high sensitivity curable resin is obtained by reacting a raw material polymer containing a main chain composed of an acidic functional group-containing constituent unit and a hydroxy group-containing constituent unit with a radical-polymerizable group-containing isocyanate compound in a ratio of above 1.0 calculated as an equivalent ratio (NCO/OH) of an isocyanate group to the hydroxyl group of the main chain. The transparency of the resin is improved, in producing the raw material polymer, by introducing the radical-polymerizable group-containing isocyanate compound by using a non-nitrile azo-based or peroxide-based polymerization initiator and/or using a polymerization inhibitor of either a compound of formula (9) or a compound of formula (15). Rise in viscosity is prevented by treating the curable resin with an alcohol. A color layer and a protecting film of a color filter and a columnar space are formed by using the curable resin.

Description

1260329 V. OBJECTS OF THE INVENTION (1) [Technical Fields of the Invention] The present invention relates to a method for producing a high-sensitivity hard and canal which is hardened by the amount of light in the curable resin. s, s re-sensitization curable resin composition, I additionally have a high degree of preservation in addition to; in the middle, in use or in the process, no county = sensitivity Stabilizing '_lipid (in the case of V, the molecular weight is increased, viscous) 'and the photohardenable tree containing the high residue and Π 子 在 在 在 在 在 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且Thick and uniform two hard two bows: Membrane which is easy to adjust the coating film with increased viscosity: this kind of high sensitivity and transparent; =; The material, the canal, etc., the ij; the sensible and transparent curable resin composition, and the present invention has a squeaking film for an anciently formed coloring layer and a protective layer of her colored layer. The spacer of the Μ or liquid day layer: the color film and the liquid day and day panel, the color filter and the case of uneven contrast.攸 页 页 页 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 。 。 。 。 。 。 。 。 In general, the liquid crystal display device process does not pass, and the electrode base of the filter substrate and the claw substrate is used. A gap portion 3 of about 1 to 10 (four) is provided therebetween, and the liquid crystal compound L is introduced into the gap portion 3, and the periphery thereof is sealed with a sealing material 4. The sheet 1 is laminated on the transparent substrate 5 in order.昼 891 891 891 21019.ptd 4 4 4 891 891 891 891 891 891 891 891 、 、 、 、 、 、 、 、 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色The principle of green color (6) and blue (8) is based on the structure of the dichroic layer 7 with the f film 8, or recently the color filter j film 8 and the transparent electrode film 9 are used from the side closer to the transparent substrate. In this order, the side of the machine, the machine f ^, in the color filter 1 and the inner surface of the electrode substrate opposite thereto: Γ (4). Further, in the gap portion 3, a bead 11' as a substrate 2; a bead diameter 11' is dispersed to maintain the gap between the color filter 1 and the electrode 于. By controlling the coloring, the color pixel or the liquid crystal layer behind the color filter f serves as an image of color. The dryness can be formed in the filter, which is a problem that may occur when the gap in the gap of the colorimetric liquid crystal display is uneven. When the space is irregular with the bead, the surrounding liquid crystal is low. To this end, the shape of the face

The color film protective film 8 is provided with a p-protective colored layer of a colored layer and a function of flattening the color filter 6 on the color filter. ^ In the device, the surface of the transparent substrate due to the color filter: the unevenness of the gap between the respective elements of R, G, and β, or the presence of each quasi-equal, detracts from the flatness of the transparent electrode 9. Uneven color or uneven contrast, and resulting in image quality, the 'protective film is required to have high flatness. , 4 pieces of g-shaped government figure 1 is not the particle-shaped bead 1 1 field person behind the black matrix layer 6 or behind the vegan without ^ |

Disperse. When the bead is placed in the display area, that is, the light of the backlight of the f-book will pass through the part of the bead, and the alignment of the =^ will also be disordered, so that the image of the display is large, as shown in Fig. 2. In place of the dispersed beads, in the region where the color filter m Ρι is in the position where the black matrix layer 6 is overlapped, the shape is formed

1260329

V. INSTRUCTIONS (3) The cell gap is protected by the above-mentioned protection, and the colored black matrix layer on the board of the material part is protected by the use of grease, and the coating is exposed. It can be known as a base after about 20,000. This resin is more difficult to use due to the use of the film, and the thinner case should be the column spacer 12 . The columnar spacer 12 can be formed using a resin. If the test is axillary or male-closed, the protective film 8 should only be covered with a transparent base. Further, the columnar spacers 1 2 are necessarily provided in the y-region, that is, in the non-display region. The photocurable resin film and the column spacer which are easy to define the region to be hardened by the photomask. When the photocurable resin or the columnar spacer is used to develop a photocurable resin and then an organic solvent, it is troublesome to handle it by treatment and waste liquid, which is disadvantageous in terms of economy and stability. A photocurable resin which exhibits an image by introducing an acidic group into a photocurable resin has been developed. The tempering photocurable resin, for example, has a weight average molecular weight = cresol novolac epoxy acrylate, etc., which has a predetermined alkali solubility of a decanoic acid group. However, since the monomer component of the tree is a sulphur-based acryl-based group, the composition is low, and for example, the residual monomer unit is dissolved in the liquid crystal portion, and the amount of elution during alkali development is increased. Further, in order to impart photocurability, a method of polymerizing a radical of a propylene group or the like into a molecular structure is known, for example, to make an isocyanate and a diol thereof. The reaction of the isocyanate group at the terminal is prepared, and the isocyanate group of the reactant is reacted with 2-hydroxyethyl hydrazide of methacrylic acid to form an amino phthalate ester ester, thereby being at the end.

1260329 V. Description of Invention (4) = Method for radically polymerizable groups such as a group of alkene groups. According to this method, in principle, only the two end groups of the molecular structure are acryl groups. Further, it is also considered that a radically polymerizable compound having one or more molecules of (meth)acrylinyl group or the like contains -(tetra)1 as a method of radical polymerization, but this cannot be achieved by: The content of the base is a problem of gelation and the like. As described above, although the protective spacer for forming the color filter using the photocurable resin is convenient, in the conventional photocurable resin, the soluble group or the (meth) acrylonitrile group or the like is determined.

The amount, considering its hardenability, solubility, etc., is difficult to control.牛别令[Solution of the Invention] According to the undisclosed knowledge obtained by the applicant's research, the main chain consisting of the unit of formula (1) and the constituent unit of the following formula (2), eight (5), isocyanic acid (f Acrylic acid & s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s (4) The amount of the brewing base can be freely adjusted, so it is very suitable as a photocurable resin. Formula (1)

R

I one (CH2 - C) one

I c==〇

I

OH

89121019.ptd $7

89121019.ptd 1260329 V. Description of invention (5) Equation (2) (CH2 - C) C=0

0 R II I OCN-R4-〇-C~C=CH2 (In each formula, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R1 represents a carbon number of 2 to 4 alkyl groups, and R4 represents an alkyl group. , R5 is hydrogen or methyl). However, the sensitivity of the film or pattern for forming a hardened resin using the above copolymer resin is required to be improved so that the copolymer resin can be hardened rapidly even with a small amount of exposure. Further, the applicant has confirmed that when the above copolymer resin is dissolved or dispersed in a solvent, the molecular weight is rapidly increased to increase the viscosity. This layer of stickiness is confirmed by the applicant, etc., even at room temperature, and the higher the storage temperature, the higher the temperature. Also, using Gpc (Gel

In one experiment of Permeation Chronatography (gel permeation chromatography), only the above copolymer resin was dissolved in a solvent and stored at room temperature for 2 weeks, so that the molecular weight of 6900 was increased to 98 在 at the time of preparation. 1', and the viscosity of the solution also reached 1. 1 7. Further, when the copolymer resin was stored at 70 ° C for 3 曰i 丄, it was found to be 6 900 at the time of preparation (the molecular weight of 1 was increased to 340 0 0 , which also increased to 1.14 times. Further, this copolymer resin Mix and dissolve with thermosetting grease, acrylic monomer, polymerization initiator, etc. i^· Page 8

1260329 V. INSTRUCTIONS (6) In the case of solvents, the viscosity phenomenon is intrinsic, so the film thickness, especially the height of the filter, or the protective film is matched with the two-dimensional size change on the black matrix. Column spacers His mechanical properties The photohardenability of the film or column is marked by the actual use step. The preservation property, the color of the easy-to-color film, and the formation of the ensuring liquid have a very high formation in a composite layer, and therefore, when the shape of the coating is also deteriorated, the composition of the tree is also thickened. . The copolymerization of the coating liquid is such that the film thickness of the coating layer is generated, and the accuracy of the single height of the crystal panel and the region in the region are intermittently deteriorated by the resin for the coating liquid. Therefore, it will be that the coating liquid in the columnar state will retain the fat due to uneven coverage of the element gap - the ten-story continues to form and the viscosity is used as the inter-color filter spacer. In the case of storage, the column of the colored layer is caused by this. Compared with the increase of the thickness of the columnar color layer, the color of the sub-component 4 匕 spacers contains the above-mentioned combination, and it is necessary to confirm that the protective film spacer of the reinforced and viscous viscous layer is twice as large as the coloring layer spacer, which is easy to incur In the case where the strength or the layer thereof or the protective copolymer resin is strongly resistant to the resin for forming the coloring layer or the protective layer of the color filter, it is required to have good transparency. However, according to the knowledge and insights of the inventors, the above copolymer resin does not necessarily have sufficient transparency.

The present invention has been developed in view of such circumstances, and its first object is to provide a method for improving the sensitivity of the above-mentioned curable copolymer resin, and a curable resin having a higher sensitivity than that of the present invention. The second object of the present invention is to provide a method for improving the storage stability and stability in addition to the improvement of the sensitivity of the curable copolymer resin, and a hardening property which is higher in sensitivity and less likely to cause an increase in viscosity than today. tree

89121019.ptd Page 9 1260329 V. INSTRUCTIONS (7) Grease. The third object of the present invention is to improve the sensitivity of the resin, and to improve the transparency and transparency. The fourth object of the present invention is to achieve the high-intensity hardenability of the resin. A color filter composed of a chemical resin composition to form a protective member and a liquid crystal panel. [Means for Solving the Problem] The high-sensitivity-curable resin according to the present invention is characterized in that at least one portion of at least a part of the acidic functional group of the isocyanate is contained by a main isocyanate compound having at least a constituent unit having a hydroxyl group. The fraction of the radical-containing polymerizable group in the above-mentioned main chain is equal to or higher than 1 〇. The sensitivity of the resin is introduced at a high ratio by adjusting the radical-polymerizable group to the side chain of the above equivalent ratio (NC0/0H). Further, the content of the constituent unit of the high functional group of the present invention provides a method which can be improved in addition to the above-mentioned curable copolymerizability, and a more preferred curable resin. k is a composition comprising the above modified hard fat. Provided is a columnar spacer resin using the above-mentioned modified hard coat film and/or cell gap, characterized in that the constituent unit of the hardened acidic functional group and the compound having a radical and a polymerizable group are provided The isocyanate group is composed of a polymer which is bonded to the above guanamine and/or combined with the above hydroxyester; the amount of the compound of the cyanate S is the equivalent ratio of the isocyanic acid® base (NC〇r When the amount of the isocyanate S-containing compound is 1.0 or more, the radical polymerizable resin can be added, and the curable tree-like curable resin can be improved, and the acidity can be adjusted to an appropriate ratio to adjust the alkali.

89121019.ptd Page 10 1260329 V. Description of invention (8) " - Soluble (developing). In the above division I, the above equivalent ratio (NC〇/〇H) of the isomeric acid § is adjusted to 丨·〇 to u. The content ratio of the constituent unit having the radical group is adjusted to be at least 1 part by volume based on the amount of charge. By introducing the above-mentioned equivalent ratio (NC0/0H) of the isocyanate group to 1.0 or more, the introduction ratio of the isocyanate group is increased, and the charge amount of the constituent unit having t ^ is set to 14 mol% or more, and isocyanate group. Since the part of a, ^ is increased, the side chain of the radical polymerizable group can be introduced into the photocurable polymer in a small amount, and a particularly high sensitivity can be obtained.

The upper limit of the amount of the isocyanate compound of the radically polymerizable group is such that the above equivalent ratio (NC〇/〇H) of the isocyanate group is 2 〇 to the ratio of 5 liters to the animal (NC0/0H) When it is 2 or more, the unreacted radical polymerizable group-containing isocyanate compound of the curable resin remains in a large amount, and the physical properties of the curable resin are lowered.

In the curable resin of the present invention, an unreacted radical-containing polymerizable isocyanate compound is also mixed. The amount of the radically polymerizable group-containing phthalocyanate compound which is actually introduced into the side chain by the photohardenable polymer which is an essential component of the curable resin can be measured by 1H-NMR. After the curable resin of the present invention is subjected to a method such as a reprecipitation purification method to remove a component having a weight average molecular weight of 5,000 or less in terms of polystyrene, a radical containing a high molecular weight portion of the photocurable polymer is introduced. When the double bond of the polymerizable group isocyanate compound is measured by iH_NMR, the amount of the residue of the radically polymerizable group-containing isocyanate compound per unit of the main chain is up to 8 mol in the present invention. A method for producing a sensitizing curable resin is characterized in that

1260329 V. Inventive Note (9) In the case of a raw material having a main chain composed of a constituent unit having at least an acidic functional group, an isocyanate compound having a hydroxyl group and a hydroxyl group-containing compound are converted into a base group. The equivalent ratio (10) of the acyl ester group is in contact with the oxime chain rate and the base of the above-mentioned manufacturing method in the above-mentioned manufacturing method. Or disperse in a solution formed in a solvent to dissolve the bismuth;丄 含 含 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异 异Under the condition that the amount of the liquid compound is small, 1 is the same as the ratio of the acid ducklings (the ratio of NCO/OH^.o is still easy: the hardening property of the cyanide acid sensitivity) Resin. X is transmitted to & ί i : I :. For a main body, the main chain is composed of an acidic group: base = early position and a constituent unit having a radical; The acid vinegar compound reacts with it and then reacts with the alcohol to improve the high sensibility. #Measure the high-sensitivity resin of the alcohol treated body, which has the alcohol 1:--the base and the still The at least one of the acidic functional groups of the main chain of the sensory resin: the molecular structure of the concealed. If the high-sensitivity resin is treated with an alcohol, the retention is improved because of the increase in the temperature of the coating. It is easy to produce uneven coating. Take ϋ明: 'Polymerization of raw materials for curing resins When the photocurable portion is formed, it is preferable to use a non-nitrile hydrazine hydration initiator or a peroxide polymerization initiator as a polymerization initiation.

89121019.ptd Page 12 1260329 V. INSTRUCTION OF THE INVENTION (10) In the case of radical polymerization, a reaction component which exhibits a high optical resin among the polymerization-initiating curable resins which are determined by the polymerization formula (1 5 ) is a small amount. Therefore, it is preferred to use a compound selected from the phenolic compound of the following formula (9) and a compound of a lower ester compound in the light-transmissive (9)-based isocyanate compound and the original polymer reaction initiator. In the case where the above specific agent and/or the above specific polymerization inhibitor are used to form high sensitivity, the obtained reaction liquid has a transmittance in the visible region and the ultraviolet region. Therefore, even if it is used as a coating liquid without purifying the high-sensitivity hardening liquid, it is colored to form a film having excellent transparency, and since the ultraviolet ray has a high ultraviolet ray rate, the exposure sensitivity is also good.

(wherein R6 represents hydrogen, an alkyl group having a carbon number of 1 to 5 or the following formula (10): formula (10)

OH

R8 R9, (D in the formula (10) -S-, an alkyl group having a carbon number of 1 to 10 or an alkylidene group having a carbon number of 1 to 10; an alkyl group having a carbon number of 1 to 10 in the R7; R8 Table hydrogen, an alkyl group having a carbon number of 1 to 10, or the following formula (11):

89121019.ptd Page 13 1260329 V. Description of invention (11)

^ (11)

R in the formula (11), R1G, carbon number gl~1〇 alkyl or carbon number i~ι〇, R9, hydrogen or carbon number i~丨〇 alkyl; only... and ... At least one dollar ϋϊίΤίί has a cyclohexyl group; x, the same - symbol:: the base system can be the same or different) n Formula (15) ', (

Rn

P

(wherein 'R11 represents hydrogen or an alkyl group having 1 to 2 carbon atoms). By using the above polymerization initiator and/or a specific polymerization inhibitor,

For example, the reaction solution of the high-sensitivity hardening resin is diluted with acetic acid 3-indene butyl ester or the high-sensitivity hardening resin separated from the reaction liquid is dissolved in ethyl lactic acid 3-methoxybutyl ester to prepare The resin solid is divided into 2 〇% by weight of the acid-3-methoxybutyl ester solution, and when the prepared solution is placed in a lcm-divided quartz cell, the light transmittance of the visible region of 4 〇〇 nm is 6 〇% or more, or the light transmittance of the ultraviolet region of 360 nm is 5〇% or more. The curable resin composition according to the present invention is characterized in that the high-sensitivity curable resin is contained as an essential component. The curable resin composition of the present invention can maintain the excellent properties of the high-sensitivity resin which is an essential component as it is. That is, because the amount of exposure can be reduced in a short time

89121019.ptd Page 14 1260329 V. INSTRUCTIONS (12) Hardening, so the film formation is highly productive. Further, due to the alcohol treatment of the #^ resin, the increase in viscosity is unlikely to occur, and since the control is excellent in the control of the hardness of the sensation, a uniform thickness of the coating film = the pattern of the preservation or coating can be obtained. Further, it is also possible to form a film having excellent transparency and a good size. According to the present invention, it is possible to obtain a very high-quality product obtained by coating the coating film formed by applying the curable resin composition to the bismuth curable resin group, and measuring the film thickness (development; The film is pre-baked by the pre-baked coating film for post-baking, and the film thickness is determined according to the following formula: Qiao Dudan & film thickness (final hard residual film rate w after final hardening) Film thickness + imaging _

X 100 μ J Determination of residual film rate; 定:: parting = composition '...residual film rate after hardening, the exposure will be pre-baked coating film is also completely film / · &, joy, film thickness (completely exposing the film thickness), and subjecting the exposed ΐ 4 i ΐ ι ΐ imaging step to the condition for determining the residual film rate for ί=ί film thickness (final hardened film thickness), Formula: The final film thickness of the second film without the imaging step (at 111) + the full exposure film thickness (//m)) χ 1〇〇 determines the reference residual film rate; and will be Φ + . ^ The residual film rate of rs...^ ® is the same as the beam 'i, jF,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 100mJ/cm2. ’

1260329 V. INSTRUCTIONS (13) The color layer of the too-named film obtained according to this, covered with: :: m into 4 do not 'column suitable for forming the cell gap of the color filter;;::, and for The coloring layer and the protective film of the liquid crystal surface are maintained;::: A columnar spacer having a desired film thickness [embodiment of the invention] / twist is formed. The invention provides a modified tree wax having an acidic functional group, which comprises: an isocyanate group composed of at least a main chain and a unit comprising a radical; κ: group t; The single::, cyanate compound is formed by a polycondensation polymer having at least a part of the reaction mixture 2i:L: an acidic functional group or a base having an acidic functional group. And the ratio of 坰^ is reduced by the curable resin, and is used to make the single-component body used in the chain of acidic functional group solubility level into the early lead polymer main compound. . The acidity of 1 ί /, which has a double bond group and the acidity # H contribution, is usually a carboxyl group, and if it is a ": A ^, it can also be a group other than a carboxyl group. It has a role in alkali imaging. It has the acidic functional A soil constituent unit. - The composition of the base is 'the early formula' (1), the formula (1) y does not match ~ (CH2-C) — c=o

OH (the hydrogen in the formula or the alkyl group having a carbon number of 1 to 5) 89121019.ptd Page 16 1260329 V. Description of the invention (14) The formula (1) and the other formulas described later are octadecyl groups. As the alkyl group, R'-based hydrogen of 3, or a group having a carbon number of 1 to 5, n-butyl, isobutyl, thiol-ethyl, n-propyl*, and isopropyl can be used as the formula (1). The constituent unit is a base group, a tributyl group, a n-pentyl group and the like. The monomer of acid, methacrylic acid or 2-mercapto~1 can be exemplified by propylene, 1-carboxy-p-heptene, etc., such as butyl-1-hexene, etc. - Carboxylic acid has a constituent unit of a hydroxyl group, and has few components. φ is a side chain of a radically polymerizable group containing a radical polymerizable group in a compound-partial group, a radical-polymerizable gas group, and a main chain The acid functional group reacts and the majority of the acid vinegar compound is: a side chain of the isocyanato group containing a radical polymerizable group. The radical polymerization of the chain; the radical polymerization of the chain can be obtained according to the required light;;: the ratio of the composition of the base is set to the extent of the first degree of compatibility. As the monomer having a double bond group and a hydroxyl group, a compound having a double bond group and a hydroxyl group can be used as a monomer having a "* early position in the polymer main chain." As a constituent unit having a search base, it is preferably represented by the following formula (2). Constituent unit 0 Ρ Formula (2) | —(CH2 — c) A c=o 〇 (wherein R is as defined in the equation 八丄, R1 is a carbon of 0i mesh 2~4). The R1 contained in the work is an alkylene group having a carbon number of 2 to 4, and is exemplified by a stretched B. 1260329. 5. Inventive Description (15) - -- a propyl group, a butyl group, and the like. As an early body, an example of which is acrylic acid 2- _ $ US & Y constitutes an early olefinic 2-hydroxypropyl ester, fluorenyl ^ _ industrial ethyl ester, propyl methacrylic acid 4- butyl ..., C The main chain of the dilute acid 4-butyl vinegar and the oxime-based polymer contains: a composition unit of the formula (7) having a late position and a radical (7): "Alkeny:" may also contain other copolymerization components. For example, the copolymerization of ":: a constituent unit of a fragrance carbocyclic ring and/or a coating film having a protective film containing a color patch on the brewing chain,

: It is a product for the filming property of a constituent unit having an aromatic carbon ring. In the early stage, a constituent unit having an aromatic carbon ring containing a double bond group and an aromatic carbon ring is used, and it is preferable to constitute an early position. (3) is not the formula (3)

R

I (CH 2 C) is a formula wherein R is the same as the above, and R 2 represents an aromatic carbocyclic ring. The R2 aromatic carbon ring contained in the '3' can be, for example, J. As a unit for expressing the formula (3): base or naphthalene, " phenyl benzene... The aromatic J body can be 3 benzene, ruthenium, bromine, etc.

89121019.ptd Page 18 1260329 V. Inventive Note (16) Halogen atom, methyl group, r its guanamine group, etc. Gan. Ethyl group 4 alkyl group, amine group, month base group, mouse base, enemy Base, sulphuric acid « ^ ^ ^ ^ & scaly acid and so on. /, the constituent unit of the preparation base is a suppression hardening component. A compound having a main component comprising a double bond A V conjugate as a base having a structure in which an ester group is provided can be used as a base material; Bit. / into the early position ' $ is the composition shown in the following formula (4)

(10) R

I —(CH2 —c)—

I 00 〇 R3 (wherein R is an episulfide group or an aryl group contained in the above formula (4)). The alkyl group, the benzyl group, the phenylene group, the ' or the aryl group, and the aryl group such as a monoethyl group in which the carbon number is 1 to 1 2 is formed. As the ethyl acrylate of the formula (4), (j, j, for example, methyl (meth) acrylate, (methyl) ketone, (meth) propylene heart = butyl vinegar, (τ base) ) Dicyclopentyl acrylate, ethyl hexyl hexanoate, (cyclohexane, C methyl) hexyl hexyl acrylate, isobornyl (meth) acrylate, (di) pentylene ethyl acrylate (Methyl) propyl ester (meth) benzyl benzyl acrylate, phenyl acetoxime (meth) acrylate acrylate). Used to put the formula (丨) ~ (b) in the future. The monomer of the chain may be an example in which each of the constituent units is exemplified by the main unit of the photocurable polymer introduced into the unit (4).

89121019.ptd 1260329 V. Description of invention (17) It is possible to use two or more types. In the main chain composed of the above constituent units, the radical polymerizable group-containing isocyanate compound is bonded to at least a part of the isocyanate group and at least a part of the acidic functional group, and/or at least one of the above hydroxyl groups. Part of the amine phthalate is combined to form a side chain of a radical polymerizable group. As the isocyanate compound containing a radical polymerizable group, isocyanate (mercapto) propylene oxyalkylate of the formula (5) can be used. Further, (meth)acrylation in the present invention means any one of an acrylic group or a mercaptoacryl group, and the (mercapto)acryloyl group means any one of an alkylene group or a mercaptoalkyl group. By. Formula (5)

0 R

11 I

OCN — R 4 —〇 C—C=CH (In each formula, R 4 represents an alkyl group, R 5 represents a hydrogen or a fluorenyl group). In the isocyanate (fluorenyl) propylene oxyalkylene ester of the formula (5), it is preferred that the (fluorenyl) acrylonitrile group is bonded to the isocyanate group (-NC0) via a carbon number of 2 to 6 alkyl groups. By. Specific examples thereof include 2-acryloyloxyethyl isocyanate and 2-methylpropenylethyl isocyanate. The ethyl 2-mercaptopropenyl phthalocyanate is commercially available, for example, under the trade name "Karenz MO I" manufactured by Showa Denko Co., Ltd. In the curable resin of the present invention, the content of each constituent unit of the main chain is a monomer for forming a main chain and an isocyanate compound containing a radical polymerizable group.

89121019.ptd Page 20 1260329 V. INSTRUCTIONS (18) ::: The amount of 吏 (total amount of mash) is the whole valley as shown below. The ratio of the clothing is the first, the formula with the acidic functional group (the ratio of the early base of the above-mentioned required alkali solubility is usually from 5 mol% to 55 mol and 5 weeks). In the section, the amount of the metering ear is %. The molar %, preferably the U molar %~30, has the degree of the hydroxy group (2) and the degree of conformity (sensitivity) of the constituent unit is adjusted. It is required to be 4 ears % to 95 % by mole, preferably 14 moles ^ 4 in summer, usually a unit is introduced into a radical polymerizable group: 5 dimol %. Even if the relative hydroxy group is increased, the high sensitivity is not obtained when the ratio of the ratio of the hydroxy group is too large. When the number of constituent units of the diradical polymerizable hydroxy group is too large, it is difficult to synthesize the resin. Therefore, the hardening property of the aromatic ring type (3) constitutes the enthalpy of the unit, and when expressed in terms of the amount of charge, the ratio is applied, and the coating is adjusted to 5 mol% to 50 mol%. Mole % to 75 mol%, preferably having a ratio of the constituent units of the formula (4) having an ester group. Imaging, when the amount of charge is expressed, #羊, in order to respond to the necessary %, should be 5 mol% ~ 50 mol%. Two for the mol% ~ 75 mol of the present invention, containing free radical polymerization It is an increase in the curable resin ;; = compound 'isocyanate containing a radical polymerizable group VIII!: The amount of the main chain of the present invention relative to the photocurable polymer, converted to the isocyanate group of the Yin Gong Juan page 21 89] 2]_.Pid 1260329 V. Description of invention (19)

The § ratio (N C 0 / 0 Η) is adjusted to be more than 1 · Q (that is, equal to or greater than the equivalent). The amount of the hydroxyl group is calculated from the amount of the hydroxyl group in the unit of the formula (2) having the hydroxyl group, and the amount of the isocyanate group is calculated from the amount of the isocyanate group of the radical polymerizable group-containing isocyanate compound. The calculated value is derived from the above ratio = (NC0/0H). By setting the equivalent ratio (NC〇/〇H) to 1 〇 or more and smashing to 1.2 or more, the side chain of the radical polymerizable group can be introduced at a high ratio, and the sensitivity of the curable resin can be improved. In addition, it is preferable to adjust the above-mentioned equivalent ratio (N(3)/〇H) of the isocyanate group to 〇 or more, and it is preferable to set the content ratio of the unit of the formula (2) having a hydroxyl group to 14 mol% or more in the f-material. . By adjusting the above animal ratio (NC0/0H) of the isocyanate group to 1 Å or more, the introduction ratio of the isocyanate group can be increased. At the same time, by setting the charge amount of the constituent unit having the radical group to 1 4 mol% or more, the isocyanate group-reactive portion is increased, so that the side chain of the radical-bonding group can be introduced into the light in a very large amount. A hardening polymer gives a particularly high sensitivity. The upper limit of the amount of the isocyanate compound containing the radical polymerizable group is preferably such that the equivalent ratio (NC〇/〇H) of the above isocyanate group is 2 Å or less. When the equivalent ratio (NC0/0H) exceeds 〇, the amount of the isocyanate compound which does not react with the radical polymerizable group in the curable resin remains in a large amount, and the physical properties of the coating film formed by the curable resin are lowered. In the case where the curable resin is viscous and the alcohol treatment described later is carried out, the isocyanate group of the radically polymerizable group-containing isocyanate e-form which remains in the unreacted t ^ is reacted with an alcohol. A part of the base polymerizable group remains. So single

1260329

89121019.ptd Page 23 1260329 V. INSTRUCTIONS (21) Mercapto-2, 5 1,1,3,3 -tetramethylbutyl ester, amber ruthenium peroxide, 2,5 bis (2-methyl peroxide) Hexane, hexane, 2-ethylhexanoic acid, cyclohexyl-1-ylethyl ester, 3-hexyl peroxy-2-ethylhexanoate, 4-mercaptobenzoquinone peroxide, benzoyl peroxide An organic peroxide (peroxide-based polymerization initiator) such as hydrazine, 1, fluorene-di(t-butylperoxy)cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it can be used in combination with a reducing agent as a redox polymerization initiator. In order to adjust the weight average molecular weight in the production of the base polymer, a molecular weight modifier can be used. For example, halogenated hydrocarbons such as gas-like or tetra-carbonized carbon, mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tri-dodecyl mercaptan, and mercaptoacetic acid can be used. Xanthogenates such as dimethylxanthate disulfide and diisopropylxanthate dicarbonate, and terpinolene, fluorene-fluorenyl styrene dimer, and the like. The base polymer may be any of a random copolymer and a block copolymer. In the production of the random copolymer, the composition of the various monomers and catalysts exemplified in the above formulas (1) to (4) may be a mixture of 2 to 10 ° C at a temperature of 2 to 10 ° C. It was dropped into a polymerization tank containing a solvent for 5 hours, and it was polymerized by aging it. The polystyrene-equivalent average molecular weight of the base polymer having the unit of the formula (1) to the formula (4) (hereinafter simply referred to as "weight average molecular weight" or "Mw" is 1 0 0 0 0 to 1 0 0 0 The range of 0 0 0, preferably the acid value is 5 mgKOH/g to 40 0 mg_/g. The reaction of the base polymer with the isocyanate compound containing a radical polymerizable group can be contained in the presence of a small amount of catalyst. Free radical polymerizable group

89121019.ptd Page 24 1260329 V: Inventive Note (22) ^ ® 曰 compound is put into the inter-segment reaction once, or one by one is dibutyltin laurate, this base, hydroquinone, naphthylamine A polymerization inhibitor such as a third slant to a s s. In the reaction, if the conditions of the free radical polymerizable group are different, that is, the conditions of the free radical polymerizable group, that is, the vicinity of the isocyanic acid relative to the hydroxyl group, it is still easy to obtain, When the reaction system is combined, the isocyanate group is difficult to initiate with respect to the hydroxyl group. On the other hand, when the amount of radicals is once added to the dissolution of the base polymer (primary input method), the amount of the resin is compared with the charge of the isocyanate compound. Therefore, the amount of isocyanate contained in the main chain of the isocyanate compound charged in one pass is 1.2 or more. The acidic functional group in the isocyanato group containing a radical polymerizable group is a unit of the formula (1), and a part thereof; 5 is carried out in a manner in which the raw material polymer solution is continuously dropped. As a catalyst, if necessary, a solution of p-nonoxy catechol and a 2,3-di-t-butyl-based polymerizable isocyanate compound (dropping method), that is, cyanic acid can be used. The equivalent ratio (NC0/0H) of the ester group having a small charge amount of the vinegar compound is 1. A high-sensitivity hardening resin. The reason is that a small amount of an isocyanate group field is preferentially reacted, and a useless isocyanate group is used in the entire solution of the compound, and the reaction is continued for a certain period of time. A slightly more base is easier to obtain a high-sensitivity hardening method. The radical-containing polymerizable group 'is equivalent to the equivalent ratio (NC0/0H) of the photocurable polymer, and it is preferable to adjust the acid S-based compound to the base polymer oleic acid amide group. For example, [ώ二* oxidized carbon gas by guanamine bond

1260329 V. INSTRUCTIONS (23) Combine and form a unit as shown in the following formula (6). On the other hand, the isocyanate compound of the ruthenium radical ♦ conjugate group is, for example, the acetonic acid acetate group as the amino carboxylic acid core: the constituent unit of the formula (2), The formation reaction is bonded by an amino phthalate bond = a constituent unit represented by a unit of the following formula (7).

R

I (CH 2 - C)—

I 〒 2 0 OR5 I it 1

HN-R —〇一 C —C=CH2 (7)

R

I (CH 2 - C) -

I c=〇

I 〇

I 〇 0 R5

I II Λ ii I 〇 C 一 — — — C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C

(2) a unit of the formula (2) having an acidic functional group, a constituent unit having an acidic functional group: / a unit of formula (6) having a radical 2 and a radical introduced therein, and having a hydroxyl group The formula (2) constitutes a unit structure of the formula (7) having a radical polymerizable group, and the molecular structure is connected in an arbitrary order.

89121019.ptd Page 26

1260329

V. Inventive Note (24) ΐ = The reaction of the polymerizable isocyanate compound with the base group is more than 20 times higher than that of the diterpene ester compound and the acidic functional group, especially 盥 ;; 5 reaction speed. Therefore, the free two-two, the constituent unit of the hydroxyl group, and in the acid-forming early position, are introduced into one part of the acidic functional group; Will remain. Soil small mouth color: the two raw resin is used to form the color layer of the filter and color film, and the coating is the second one; the column spacer which maintains the cell gap of the liquid crystal panel is agglomerated by the gel permeation chromatography. Stupid ethylene conversion flat two ΓΪ adjustment in _ 〇 ~ 1 〇〇 ° _, should be adjusted in the range of 2 _ ~ ^ 00. When the weight average molecular weight is smaller than 1 ,, it is marked so that the pattern shape at the time of pattern exposure is difficult to control, and in the case where D ^ is used as a pattern, there is a problem that the final film thickness is reduced. 1 On the one hand, when the weight average molecular weight is larger than 1 0 0 0 0 0, the viscosity of the photoresisting day = the overhang, and the coating suitability is lowered, the developing property is deteriorated, and the pattern is not easily removed. The problem. The acid value of the cerium-curable resin is preferably from 5 mgKOH/g to 400 mgKOH/g, more preferably from 10 mgKOH/g to 2 〇〇mgK〇H/g. The acid value is related to the alkali developability, and when the acid is low, there is a problem that the development is poor, and the adhesion on the substrate and the color filter resin is insufficient. On the other hand, when the acid value is too high, the development performance is too good, and there is a problem that the pattern shape is not easily controlled when the pattern is exposed. In the curable resin, the hydroxyl value can be adjusted within the range of from 0 mgKOH/g to 200 mgKOH/g. The hydroxyl group on the main chain of the curable resin does not necessarily have to remain in the residue, but when it is left, it is adjusted to dissolve in the solvent.

89121019.ptd Page 27 1260329

The high-sensitivity hardening obtained according to the present invention is suitable for forming the coloring layer of the enamel sheet, covering the parent layer:: the special:: the columnar spacing of the cell gap of the liquid crystal panel: layer; or: quasi, Ϊ: Ξ The amount of the constituent units of the main chain and the side chain of the fat is 30. The loading amount of the constituent unit of the acidic functional group is! 0~ and 1 /, the preparation of the hydroxyl group in the early position is 15 to 19 mol%, and the loading amount of the isocyanate compound of the base polymerizable group is 18 ί*^Γ^^90^ 120^ΚΟΗ/β ? The ten-fold force is 30,000~60000 〇

The high-sensitivity hardening resin (7) obtained by the present invention = an acetoic acid-containing compound containing a radical polymerizable group; and the isocyanate containing a gentleman = polymerizable group which is actually introduced as a side chain on the two-component photocurable polymer The amount of the compound can be determined by 1 H-NMR. The radical-containing polymerizable property of the photocurable polymer introduced into the high-streaked portion is obtained by dividing the curable resin into a component having a polyphenylene weight average molecular weight of 5 or less by a method such as a reprecipitation purification method. When the double bond of the isocyanate compound is measured by 1H-NMR, the residue of the radical-polymerizable group-containing isocyanate compound having a constituent unit of 1 曰 0 0 mol with respect to the main chain

The system is more than 8 moles, and if it is particularly sensitive, it can reach 丨2mol% or more. For reprecipitation purification, for example, a solution of high-sensitivity hardening resin (solid content: about 25% by weight, solvent) : 3-butoxybutyrate acetate) diluted with tetrahydrofuran, diluted into droplets of isopropanol, hexane or a mixture of the two

1260329 V. Inventive Note (26) (Isopropanol··hexane (weight ratio) 2〇〇··0~0··100), the precipitated solid may be recovered. The reaction liquid obtained by reacting the radical polymerizable group-containing isocyanate compound 2 raw material polymer may be used as a reprecipitation step by diluting it with tetrahydropyrene. In addition, the precipitated solid may be further dissolved in 3-methoxybutyl acetate, diluted with tetrahydrofuran, and the resulting dilution may be dropped into the same or different ratios of isopropanol and/or hexane alone. Or in the mixed solution y11, the precipitated solid can be recovered. Thus, the component having a molecular weight of 5,000 or less can be removed from the curable resin by repeating the reprecipitation step once or repeatedly as necessary. Knife

When the coloring layer of the color filter or the protective film of the colored layer is formed by using the high-sensitivity curable resin of the present invention, the curable resin is required to have high transparency. When a highly transparent curable resin is required, it is hardened by reacting a monomer having a double bond group and a functional group, a monomer having a double bond group and a hydroxyl group, and other monomers necessary for the reaction. When the resin is used as the main chain portion of the photocurable polymer, it is preferred to carry out polymerization by using a non-nitrile erbium polymerization initiator or a peroxide polymerization initiator. As the non-nitrile azo-based or peroxide-based polymerization initiator, the above is used.

The isocyanate compound of the 13-radical polymerizable group and the raw material poly-H should be used as a polymerization inhibitor, and a specific phenolic compound or a f-stone 4 s-1 compound can also be used to improve the curable resin. Transparency. The specific phenolic polymerization inhibitor which can improve the transparency of the curable resin can be expressed by the following formula (9):

Page 29 1260329

89121019.ptd Page 30 1260329 V. INSTRUCTIONS (28) The substitution of the same symbol is a tertiary butyl group or an alkyl group having a cyclohexyl group; the base groups may be the same or different). Among the phenolic compounds represented by the above formula (9), those represented by the following formulas (1 2 ), (1 3 ) or (1 4 ) are preferably

Formula ((2) OH

R14

(wherein R12 represents hydrogen, carbon has 1 to 5 alkyl groups, R13 and R14 represents hydrogen or carbon number 1 to 10 alkyl; but at least one of R13 and R14 represents a tertiary butyl group or has a cyclohexyl group. Alkyl). A specific example of the compound of the above formula (12) is 3,5-di-t-butyl-4-hydroxyindole (BHT). Formula (13)

OH

R \5

I (wherein D represents -S-, an alkyl group having a carbon number of 1 to 10 or an alkylidene group having a carbon number of 1 to 10; R15 represents a hydrogen or an alkyl group having a carbon number of 1 to 10; and R16 represents hydrogen or carbon. Number 1

89121019.ptd Page 31 1260329 V. Description of the invention (29) Alkyl groups of R10 to 10; the substituents of the same symbol may be the same or different, at least one of which is a tertiary butyl group or a cyclohexyl group. base). Specific examples of the compound of the above formula (13) are 4,4'-thio-bis(3-indolyl-6-isobutylene S) and 4,4'-butylidene-di(3- Mercapto-6-t-butyl group). Formula (10)

OH

R1

OH

R R·

(wherein, R1G represents a carbon number of 1 to 10 alkyl or an alkyl group of 1 to 10 alkyl; R17 represents hydrogen or a carbon number of 1 to 5, R18 and R19 represents hydrogen or carbon number 1 An alkyl group of ～10; wherein at least one of R18 and R19 is a tertiary butyl group or an alkyl group having a cyclohexyl group; further, the substituents of the same symbol may be the same or different). Specific examples of the compound of the above (14) are 2,2'-methylene-bis(4-methyl-6-tert-butylphosphonium), 2,2'-arylene-di(4-ethyl) Base-6-tert-butylphenol) and 2,2'-dihydroxy-3,3'-bis(?-methyl-cyclohexyl)-5,5'-didecyldiphenylnonane. Further, a specific phosphite-based polymerization inhibitor which can improve the transparency of the curable resin can be expressed by the following formula (15):

89121019.ptd Page 32 1260329 R 11

P V. INSTRUCTION DESCRIPTION (30) Formula (15) (wherein R11 represents hydrogen or a carbon number of 1 to 2 fluorenyl). π:!: A specific example of the compound of the above formula (15) is tris(nonylphenyl) citrate.

丄L ί can be obtained by reacting a raw material containing a specific polymerization initiator with a specific polymerization inhibitor to react an isocyanurate compound containing a radical polymerizable group, thereby obtaining excellent transparency. .

When the specific polymerization initiator and/or the specific polymerization inhibitor described above are used to synthesize a curable resin, the purification step of removing the coloring component from the curable resin can be performed because the obtained reaction liquid is less colored. Simplified or completely saved %. Therefore, the reaction liquid containing a curable resin can be used as a coating liquid for forming a coloring layer or a protective film of a color filter in a state in which it is not purified. The reaction liquid containing the high-sensitivity hardening resin of the present invention may be diluted in the original form of acetic acid 3-methoxy butyl s, or the high-sensitivity hardening resin separated from the reaction liquid may be dissolved in acetic acid 3 - oxime And 20% by weight of acetic acid 3_methoxy butyl self-solution solution, when the solution prepared by the earth is placed in the quartz cell of the icm division, the light rate at 40 0 nm is more than 60%. More than 70%, with excellent transparency. Such a curable resin tends to have a light transmittance near 48 nm, and has a tendency to show a very small light transmittance. However, the transparent radical polymerizable group-containing isocyanate compound obtained by the present invention does not show this. Species

1260329 V. INSTRUCTION OF THE INVENTION (31) Under the above-mentioned measurement conditions, it is preferable to have a light transmittance of 9% or more in the vicinity of (4). I. The transparency region obtained by the present invention has a high light transmittance, which is at 45 in the field measured by the above-mentioned measurement conditions at 4 = m to 70 0 nm #g. — _』==:=, showing 7°% or more, showing 9 hearts at 500~70〇nm, which is 85%, and more preferably 95% or more. In the case of the formulation of the synthetic curable resin:::f and / or the specific polymerization inhibition zone, in the ultraviolet region of the second: also; get: ... liquid T is only in the reaction of the chemical resin as the cold cloth - even疋 Contains this hard combination, the ultraviolet light will reach the skin of the skin 2: solution to form a film, such as, will contain the present, brightening tree; improve exposure sensitivity. Diluted with butyl vinegar, or from the reaction should be dissolved in acetic acid 3-methoxy acid 3-methoxy TS to adjust the potential tree == sensitivity hardening resin in B, light transmittance at 360nm It is placed on the slot of the (10) knives 5 times, and the right screen 昱 呰々 呰々 is % or more, preferably (4) with the occlusion of the occlusion line. 36 w # & Therefore, this wavelength is attached: the length is increased. The effect is promoted, so that the exposure sensitivity is more hard of the present invention: the resin can be appropriately adjusted due to the sensitivity or the coating property for the feeling of exposure, because... There are cans for resists, especially for text: 89121019 r Page 34 1260329, invention description (32) 濩 film or column spacer for maintaining the single ^ ^ 兀 gap of the liquid crystal panel. ...,, right When the curable resin is dissolved, the molecular weight is increased by * at room temperature, and when the agent is used, even if the resin and the epoxy resin, acrylic: two or two: * harden or dissolve in the solvent Modulated light;: 2: 1 and so on: and the speed will be further marked. J% combined, the degree of sticking and The inventors have thought that the radical polymerizable group such as a sclerosing tree, not only the "3 methyl) acrylonitrile group, but also causes the viscosity increase during storage;: exposure; reaction-related, large fat solution with iH- When observed by NMR spectroscopy, it was confirmed that the stalking tree was not the cause of the increase in viscosity. Therefore, it is confirmed that the radical polymerization is obtained by observing the spectrum of the above-mentioned curable resin in the ft_ir spectrum, and the small peak around 1800-1 (111-1) disappears with an increase in viscosity. Consider this observation = ..^FT- IR ^ ^ ^ /ΛΙ X ^ C: The same acetic acid with a carboxyl group is in the form of an acid anhydride with isocyanic acid (ethyl acetate, reaction, etc. As a result, it is conceivable that [the above-mentioned curable resin has an acid group. This acid-anhydrous group is presumed to be a radical containing a radical polymerizable group; a compound which is constituted by at least a formula (1) having an acidic functional group and | θ When the polymer composed of the unit (2) is composed of a unit, that is, when the raw material compound is reacted to produce a curable resin, the result of the #cyanic acid base as a dehydrating agent 'is mainly from the acidic function in the same molecule. Deputy dehydration condensation

89121019.ptd Page 35 1260329 V. Inventions (33) Born. Further, when the resin is dissolved or dispersed in a solvent, the acid anhydride group generated in the molecule of the curable resin reacts with the hydroxyl group contained in the molecular chain of the curable resin to cause ester bonding. The hardening resin ^ $ inter-substrate bridge, so, it is speculated that the molecular weight will increase and the viscosity will rise.

Such a tackifying phenomenon can be prevented by treating the above curable resin with an alcohol. When the curable resin is treated with an alcohol, the alcohol may be added before the viscosity of the solution starts to rise or before the viscosity rises, in the solution in which the curable resin is dissolved or dispersed in a solvent. Further, each monomer may be polymerized in a synthetic solvent of MBA-(3-methoxybutyl acetate, CH3CH(〇CH3)CH2CH2〇c〇ch^, etc., to synthesize a constituent unit having at least an acidic functional group. a raw material copolymer composed of a constituent unit of a hydroxyl group, which is reacted in a solution of the original::j, which is a free radical of a polymer, and reacted in the obtained raw material polymer solution, followed by Further, the addition of the alcohol may be carried out. The reaction conditions at the time of the addition are not particularly limited, and the alcohol may be added during the heat of the reverse liquid, or may be added at room temperature, and the gas may be introduced into the reaction liquid. In the solution of the resin, if it is on the 醢 夕 夕 4 4 上 上 上 上 上 上 上 上 上 上

When an alcohol of more than 5% is added, it is presumed that the alcohol competes with the hydroxyl group in the main chain of the curable resin, and the acid helmet AX ... and the water base are taken, and the acid anhydride group S is made to be made. This result is presumed to prevent the sclerosing ^ ^ , the intermolecular bridging reaction of the ϋ 树 月 ’ ’ ’ 防止 防止 防止 防止 防止 防止 防止 防止 防止 防止 防止 防止 防止 防止 防止The curable resin obtained by the treatment with the monool is presumed to be a main component of the constituent unit having an acidic functional group and the composition of the hydroxyl group having a 槿忐黾a ^ 早.

1260329 V. Inventive Note (34) Chain, and base to =; =::: an oleic acid, a group with the above acidic functional moiety as a urethane hydrazine: at least / / or above - At least the acidic functional group: two 45:: The molecular structure formed by the combination of alcohol and its base with the above-mentioned inflammatory and "sickness". As an example, for the main chain having the above formula (丨) and formula (4): (2), formula (), molecular structure of the polymer;

Η — (CH R R R c) a — (CH 2 -c)b— (CH2~C)c— c=o R2 (U 0 •i R3 R1 OH R R R C)g-H (8)

R

---(CH2 -C)e- (CH2 -C)f- (CH

I I 1 H C=0 c=0 i ! ί f0

〇H a2 B

(where R, Ri, R2, R3 are as defined above

The isocyanic acid S-based compound is used as an amine group, and the isocyanate compound containing a radical polydiradical polymerizable group - a residue of a, a, a 3 The residue. Further, a, "b, as a residue of the combination of indoleamine, B e, f, g an integer of 1 or more; each structure / table 0 or more integers, d, early hatching can be used for random copolymerization or block 89112019 .ptd Page 37 1260329 V. INSTRUCTIONS (35) Copolymerization).

It is necessary to react with the alcohol at a time when part or all of the decanoic acid anhydride group is still unreacted in the photocurable polymer. Reacting a radical polymerizable group-containing isocyanate compound with a base polymer composed of a formula (1) of at least two functional groups and a base polymer having a hydroxyl group in the formula (2), @ Immediately after the production of the curable resin, the acid anhydride group has not completely reacted with the hydroxyl group, and the viscosity rise has not yet started, so that it can react with the externally added alcohol. In addition, even if the solution of the curable resin is temporarily left at room temperature, if the viscosity rises and the temperature does not reach the end of the element, the viscosity may rise to some extent due to the residual of the unreacted acid anhydride. The degree is limited and has its effect. The type of the alcohol used for preventing the viscosity increase is not limited, and any compound having an alcoholic hydroxyl group may be used, and may contain ruthenium, osmium, S, ρ or the like. Usually the lower molecular weight is easier to handle. For example, it may be N, ^, S, [etc. or not included in the carbon number of i~20, and more specifically, such as: decyl alcohol, B-, propanol, butanol, pentanol, An alcohol solvent such as hexanol, heptanol or octanol; a solvent such as methoxyethanol or ethoxyethanol; such as methoxyethoxyethanol, ethoxyethoxyethanol or the like: Dissolve j such as ethylene glycol - shouting, diethylene glycol - shouting, ethylene glycol - C

An ether solvent such as ether or propyl alcohol; for example, (meth)acrylic acid 2-ethyl acetate, (methyl-propionic acid 2-pyridyl, (meth)acrylic acid 2_ Ding vinegar, Bu

Butene-l-xetidine, tetrahydrofurfuryl bis(methyl) acrylate, tetramethylolmethyl methacrylate, ^ _ ~ V T saturated bond (4). 1' day, i material: pentaerythritol S

89121019.ptd

1260329

V. DESCRIPTION OF THE INVENTION (36) Further, the unreacted alcohol remaining in the solution of the curable resin may be removed by an appropriate means such as re-precipitation or purification. Further, after the alcohol is added to the solution having the curability ==, it can be mixed with other materials as a coating liquid in the form of a coating agent, and in the drying step after the coating, the decyl alcohol is evaporated together with the solvent for coating. Just fine. As shown in this example, when the residual alcohol is evaporated together with other solvents, the difference between the boiling point of the alcohol and the boiling point of the mixed solvent, or the difference between the evaporation rate of the alcohol and the evaporation rate of the mixed solvent is preferably small. Ideally, there is no difference. Further, the difference between the boiling point of the alcohol and the solvent / and the difference in the evaporation rate between the alcohol and the solvent are both small. Based on this point of view, the difference between the boiling point of the alcohol and the boiling point of the mixed solvent is preferably within 75 Å, particularly preferably within 40 t:. Further, the difference between the evaporation rate of the alcohol and the evaporation rate of the solvent for coating is preferably 90 [n - Bu 〇 Ac = 1 〇〇], and particularly & preferably 30 [n - BiiOAc = 100]. The boiling point and evaporation rate of the alcohol should satisfy the above conditions: here, the evaporation rate (unit: [n -Bu〇Ac = 1〇〇]), is the basis of n-butyl alcohol (n-BuOAc) at 25 C. The evaporation rate of the gravimetric method is expressed as the evaporation rate of 1 〇 (). The amount of the alcohol used to prevent the sticking phenomenon can be appropriately adjusted in accordance with the amount of the acid anhydride contained in the curable resin. It is preferable to use an amount of i 〇 to 120% by weight of the curable resin. In order to substantially completely stop the viscosity increase of the solution of the curable resin, it is necessary to leave the reaction liquid for a certain period of time after the addition of the alcohol, and to sufficiently reduce the amount of the acid anhydride group, and to prepare the alcohol-treated polymer. The reaction solution may be left at room temperature, but it may be heated to allow the ripening to be completed in a short period of time. It is preferred to place the reaction solution in which the alcohol is added at a temperature of 30 to 170 ° C for a period of less than one hour.

1260329 V. Description of invention (37) Its ripeness. Here, for example, when the aging time at 90 t is completely stabilized by the resin, and the effect of suppressing the adhesion is thin, the photocurable resin L of the curable resin of the present invention cannot be used together with the curable resin of the main polymer. For the stagnation of the moon, and the composition of the product, the photopolymerizable acrylic brewing monomer is the same: ^ above · multi-functional, etc.: 1 dispersed in the photoresist solvent (for dilution, ^ polymerization agent) In the present invention, the curable resin is used in combination with d. The meter usually contains 5 to 80 parts by weight. /◦,宜含} 〇 Fanshidan sputum resin for solid content

When the content is more than 80% by weight, the viscosity becomes too high. °:::: The resin is lowered, and the coating is inferior. When the amount of the kinetic activity is less than 5% by weight, the viscosity is synergistic: the stability of the coating of the gastric curable resin is not sufficient, and the content of the film is less likely to occur after the coating is dried. There is a problem of impaired suitability of exposure phenomenon. In the composition of the curable resin, the α-propionic acid brewing monomer is loyal to the monomer, and the polyfunctionality of the monomer is mentioned.

(Methyl)acrylic acid diethylene glycol 8th, diyl) propylene glycol vinegar, bis(indenyl) propylene dipropylene glycol, propyl propylene glycol propylene glycol, bis(diyl) Propionate, polypropylene glycol, hydrazine, hydrazide, glycerol, methyl methacrylate, hydrazine, glycerol, glycerol τ methyl) glycerol acrylate, glycerol bis(decyl) acrylate, tetradecyl 哔 Q 一 ( (methyl) acrylic acid tetrakis(trimethyl) (diyl) propyl Alcoholic vinegar, triacetic acid, triacetic acid, pentaerythritol, 酉1 ' 丙 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Di-pentaerythritol ester I side of propane ester, decyl) acrylate

89121019.ptd

1260329 Description of invention (38) Five. This 箄忐 eight multi-functionality two: used alone or in the form of a mixture. The monomer, 12-enoate-based monomer, preferably contains at least one trifunctional or more 95% by weight of / / in a polyfunctional acrylate monomer, preferably about 3 〇 ~ diluent °, can, In the case of these polyfunctional acrylic acid vinegar monomers, as the reaction (methyl) acrylate @1^ methyl (meth) acrylate, ethyl (meth) acrylate, hydrazine, (methyl) hydrazine = brewing, (meth) acrylic acid butyl phthalate, (methyl) acrylic acid pentylene dibasic ... styrene, methyl styrene, hydrazine - B from this J and other early functional monomers. As a photopolymerization surname, in the hardening tree death =! The content of the functional acryl oxime monomer, containing 5 to 40% by weight; in the solid content ratio of 3, wt%, when appropriate, formed film When the amount of the acryl vinegar-based monomer is less than 3% by weight, it is not sufficient, and the physical strength of the bismuth acrylate vinegar-like monomer is changed to become a curable resin composition. When the value exceeds 50% by weight, the property is not charged. If the part does not = will reduce the enthalpy and there will be a flexible property to form, this ratio is also necessary, # Π: ΐ f f 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像 像There will be serious pattern formation due to partial swelling and peeling. The attacker's reattachment will hinder the other, in the composition of the curable resin of the present invention, for the purpose of chemical properties (especially for the testability), and the compound having the above epoxy group (ring =, For example, a compound having two or more rings + y 邛 in the molecule is a coating base, and an example thereof is: as 89121019.ptd Page 41 1260329 V. Invention Description (39) Double-type 'A type epoxy resin Aibiite 1 〇〇 1, 1 〇〇 2, 1 〇〇 4, 1 0 0 7 , 1 0 0 9 , 1 〇 1 〇 (manufactured by Oiled Shell), etc., as bisphenol epoxy 'fat Abbott 801 (manufactured by Oiled Shell), etc., as a novolac type ring & resin, EPPN201, 20 2 (manufactured by Nippon Kasei Co., Ltd.), Aibi Kate 154 (manufactured by Oiled Sheep Shel 1), etc. , as cresol novolac type epoxy resin e〇cn) i〇2, l〇3S, 104S, 1 0 2 0, 1 025, 1 0 2 7 (made by Nippon Kasei Co., Ltd.), Aibi Kite 180S ( Oiled Shel i made) and so on. Also exemplified are a cyclic aliphatic epoxy resin or an aliphatic polyglycidyl ether.

Among them, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, = aldehyde varnish type epoxy resins, and cresol novolak type epoxy resins. Most of the compounds having two or more epoxy groups in the two subgroups are polymers - bisphenol hydrazine or bisphenol ρ glycidyl ether, each of which is low in molecular weight... (meth)acrylic acid glycidol Low-second entangled dimethylene oxide ester, (meth) acrylate is also effective in the acrylic copolymer contained in the resin framework; ^...specialized epoxy resin, solid sling in the curable resin composition For 0~60 will be my 0/ Tian L7 person 丄Ρ* Knife flux is less than 5 weight two. Π 〇% by weight. When the epoxy resin is included. % Τ, there is no way to give a sufficient alkali resistance to the protective film. Photohardening: When the content of the dioxy resin exceeds 40% by weight, it is not available.

The stability of the hardening resin is such that the fat retention of the hardened resin is removed; ϊί; :: 'unsatisfactory... Epoxy tree effect, when the addition of the U-weight dry coating film is also fat Even in the eyes, you can show the full effect of the right and left. Epoxy tree + first. After alkali imaging does not react, and the acid remaining in the coating film 1260329 V. Description of the invention (40) The reaction is heat-treated to impart excellent durability to the coating film. As the polymerization initiator, a radical polymerizable initiator can be used. The radical polymerizable initiator can be produced, for example, by the energy of ultraviolet rays. Examples of the free radicals include benzoin, a benzophenone derivative such as benzophenone or a derivative thereof; a xanthone and a thioxanthone derivative, sulfonium chloride, and a chloromethyl group; A halogen-containing compound such as a multi-column aromatic compound, a chloromethyl heterocyclic compound or a chloromethyl benzophenone; a diterpenoid; an anthrone; a halogen-burning type; a photoreductive dye and a reduction, and a reduction-reduction type ; organic sulfides; peroxides, etc. 乂 乂 疋 I, Irgacure 184, Irgacure 369, irgagur e 651 , IrgaCUre 9 0 7 (all manufactured by Kabbat Chemical Co., Ltd.), Grand Rochaya (made by Merck), Adaka 1 7〗 7 (made by Asahi Denki Co., Ltd.), 2, 2' a ketone-based or diimidazole-based compound such as bis(o-chlorophenyl)-4,5,4,-tetraphenyl", 2,-diimidazole (manufactured by Heijin Chemical Co., Ltd.). These f-starting agents can be used in combination of two or more kinds. When two or more types are used in combination, it is preferable that they do not interfere with the absorption of the spectral characteristics.

Divided into two 3 ^ 2: 5 initiator "in the curable resin composition" in the solid knife ratio is usually 〇 1 ~ 舌 〇 / ^ A from which to take eight land · heavy / 〇, and each has 1 ~15 weight 〇 / 〇. When the amount of the initiator is less than 〇, it does not progress, and there is a tendency that the residual film ratio, the ’ 'photohardening reaction, and the like m: 2 are low in heat and chemical resistance. Will reach saturation, and ^ γA in °, the solubility of the sub-resin will be in the spin coating or the coating film will be a few # ~ crystal will precipitate, and the benefits of _, positive day, start The bad situation of the agent. The film may be roughened, etc., and the modifier may be added to the above-mentioned polyfunctional acrylic resin composition, but in the first 1260329, the invention (41) The composition of the virgin resin is dispersed or dissolved in the resin composition. ^, the place where it is stored, and before the use is expected to improve the light sensitivity of the people, the sensitizer ' should be styrene based system: U plus sensation 胄. As an example of the use of H (p-di-f-amine A: or a sulphur-based compound, which has an aminostyryl) porphyrin, 4_( & alkenyl) porphyrin, 2-(p- Diethyl 4-(p-diethylaminobenzene &#-methylaminostyryl) porphyrin, Gan, allyldiyl), 2-(p------------------------------ )—3, 3-3Η-吲哚, 2一 (oblique--7 Q to one-month female basic ethylene oxime, 2-(p-dimethylamine oxime | / aminostyryl)-3, 3 — (10)-吲

Benzobenzyl) benzo- oxime. Sit, 2-(p-diethylamine soil) ^ 暴 暴 ) 本 本 本 # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # And imidazole and the like. A fragrant i-based compound, which may be exemplified by: 7-diethylamine ethylamine: ί Λ 7 diethylamine + damper methyl coumarin, 4, 6-diamine i Bean sin 1 base Prostaglandin, 3-(2-benzimidazolyl)-7-indole, indole-dimethylamino~diethylaminocyclopenta(C)coumarin, 7-amino+trifluoro

Benzopyran; 9 g'2'/'^5, ^'611, 1〇Η_tetrahydro-8-trifluoromethyl (1) -4-Santun 曱::/ A: Qinketone, 7-Ethylamino-6-methyloxymei m laugh: fragrant sulphate, 3,4,5,3Η,6Η,10Η—tetrahydro_9—xanthine and pyranthine--(9,9&,1 - Buckle) _喧嗉-10_@同. In the case of the agent, the various additions can be used as necessary. 4. The non-surfactant or the decane coupling agent is added. ^ , 〇〇 , , 眭刎 配合 配合 配合 为 为 为 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚

1260329 V. INSTRUCTIONS (42) Polyoxyethylene alkyl ethers such as cinnamoyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene octyl phenyl ether, poly(ethylene oxide) Polyoxyethylene aryl alkyl ethers such as phenyl ether; polyethylene oxide dimers such as polyoxyethylene dilauryl ester, polyoxyethylene distearyl ester; Mecca Wags F171, 172, 173 (Daily ink System), Fu ^ de FC43 0, 431 (Sumitomo 3M system), Asahi Kaide "71 〇, Sha Furong s - 382 Λ 0%,, 104, 1 〇 5 (Xu Shi Xiaozi system) and other gas system interface Activity: Do not specialize. & 荨 surfactant amount of the compound, relative to 1 〇 ° parts by weight, preferably 2 parts by weight or less, more preferably 1 weight 1 * 4 2: ‧ Γ Γ 系 改善The substrate or the other coatings are densely burned, and the second Γ Γ 为 乙 乙 乙 乙 乙 乙 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Terpene tris(/3_methoxyethoxy)decane, ethylene triethylene ring etched m ^ r decyl decane oxime. Also, as decyl acrylate, = methylmethyl hydrazine Oxyl money, r methacryloxyne involuent τ-based-methyl ketone-based sputum 箄. 祚 片 片 4 4 4 4 4 4 4 4 4 4 4 4 4 4 , , , , , , , , , , , , , , , ^ ^ Τ 丞 丞 、 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 可 可 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳 乳n-Phenylethyl)-r-r-aminopropyltrimethyl decyl decane, N-Wan (aminoethyl)- decane, 7-amine US July propyl propyl methyl dimethyl emulsion Trimethyl gas i 々 矽 矽 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .ptd Page 45 1260329 V. INSTRUCTIONS (43) Gas propyl sulfhydryl triterpene and the like. The curability of the present invention generally includes a cellulosic solvent such as a dissolved alcohol or isopropyl alcohol; a carbitol solvent; ethyl ethoxy butyl ketone, cyclohexanone oxyethyl ester, and an acetic acid oxy group. Ethoxyethoxylated ester solvent; ether solvate such as diethyl ether or the lactone solvent solvent such as N-methylpyrrole; n-heptane, organic solvent. Ethyl ethoxide, such as lytic acid; ethyl acetate such as acetoxyacetic acid carbitol diol diethyl ether, ethyl decyl butyl acrylate, CH 3 decyl ether acetate, CHq oxy stone In the composition of the sylvestre and 7-chloropropylmethyldiethoxylate resin, a coating agent and a coating suitable agent are considered, and examples thereof include a decyl alcohol, an ethanol, and a n-propanol solvent; An ester solvent such as methoxyethoxyethanol or ethoxyethoxyethanol such as ethoxyethanol or ethyl acetate, butyl acetate, methyl methoxypropionate or ethyl lactate; acetone a ketone solvent having a different methyl group; a cellosolve acetate such as methoxyethyl acetate or ethyl eluronate acetate; an acetic acid card such as acetic acid methyl acetate or ethoxyethoxyethyl acetate Alcohol, ethylene glycol dimethyl ether, diglyme, tetrahydrool; NN-dimercaptocaramine, N,N-didecylacetone, and the like; T-butyrolactone; particularly suitable for use in unsaturated hydrocarbons such as benzene, toluene, diphenylbenzene, and naphthalene, such as saturated hydrocarbon solvents such as n-hexane and n-octane. It is a solvent such as lytic acetate ester of ethoxyethyl acetate or ethyl ethoxyacetate, such as ethoxyethoxyacetate or ethoxyethoxyethyl acetate; ethylene glycol dioxime ether; An glyceryl dimethyl ether or a propyl ether solvent; an ester solvent such as methyl methoxypropionate or ethoxypropionic acid. Particularly useful are MBA (3-CH(0CH3)CH2CH20C0CH3 acetate), PGMEA (propylene glycol-OCH2CH(CH3)OCOCH3), DMDG (diethylene glycol dioxime)

89121019.ptd Page 46 1260329 V. INSTRUCTIONS

_, ICOC^OCH3) or a mixture of channels, etc., using these solvents to adjust the solid concentration to 5 to 50% by weight. Xi

As one method for producing the curable resin composition of the present invention, first, each monomer is reacted in a solvent oxime for synthesis of MBA (3-methoxybutyl acetate) to synthesize a base polymer. Next, in the solution of the obtained raw material polymer, the equivalent ratio (NC0/0H) of the hydroxyl group contained in the main chain of the raw material polymer is 1·〇 or more. The isomeric acid sulfonic acid compound of the base polymer group reacts to form a curable resin (photocurable polymer). Further, when the transparency of the resin or the ultraviolet ray permeability is particularly required, as described above, a raw material polymer is produced using a non-nitrile azo-based or an over-oxide-based polymerization initiator, and the formula (a) is used. Or a polymerization inhibitor represented by the type of sheep (15) is introduced into a radically polymerizable group-containing isocyanate compound. Then, an alcohol is added to the reaction liquid containing the curable resin, and the curable resin treated with the alcohol is heated and aged, for example, at a temperature of 3 Torr to 170 ° C for 72 hours or less. Thereafter, the reaction solution was mixed with other photoresist materials in a solvent such as MBA, PGMEA, or DMDG. The solid content concentration in the curable resin composition is usually in the range of 5 to 85% by weight.

When the curable resin (photocurable polymer) of the present invention is mixed and dissolved in a solvent in combination with another coating material, the viscosity-increasing phenomenon becomes more remarkable than the single solution liquid of the curable resin. Therefore, if the individual solutions of the curable resin are compared, the viscosity-increasing phenomenon becomes more remarkable. Therefore, when the curable resin is mixed with other materials to prepare a curable resin composition, it is particularly preferable to treat the curable resin alcohol, and then leave it for a certain period of time or heat to make it fully cooked. Material mixing.

89121019.ptd Page 47 1260329 V. Description of invention (45) '~"

The alcohol which reacts with the curable resin preferably has an evaporation rate which is close to the end point of the solvent for the preparation of the coating liquid or, as close as possible, the boiling point and the speed of the hair. More specifically, the difference between the boiling point of the alcohol and the point of the solvent for the coating liquid is 75. Within 〇, especially at 4〇. Within 〇, and/or the difference between the evaporation rate of the alcohol and the evaporation rate of the coating liquid is within 9 〇 [11 -Bu〇Ap 100] j, particularly preferably 30 [n-BuOAc = 100]. When the boiling rate of the alcohol = or the bursting speed is close to the solvent of the coating liquid, even if the alcohol remains in the curable dendrimer composition, the alcohol evaporates together with the solvent for the coating liquid, so that uneven coating is less likely to occur. situation. Since pentanol has a boiling point and evaporation rate with XP, or it is suitable, it is preferable to use a hardening tree: a treatment, and then a mixture of these materials as a photoresist. System: a modified resin composition. Since pentanol has an i-point and a bursting speed with ΜβΑ, it is particularly preferable to use yttrium as a combination == yttrium for the use of pentanol as an alcohol-treated curable resin group 2 as a photoresist. The solvent causes the curable resin composition of the invention to be "high-sensitivity hard or very short exposure"

The energy source for exposure of the present invention. Light sensitivity. First, in the method of 4, the exposure of the curable resin composition is required to be dried and shaped; the composition of the bismuth resin is used, and the substrate is exposed to the exposure, etc.: the substrate is as long as it is transparent.颂'荨A series of pattern formation steps are not

89121019.ptd Page 48 1260329

The base Mu I who can cause problems can be used without problems. Coated 臌 - no special restrictions, through the soil ‘the thick sound of the moon, the limb A $ A k Μ is the thickness of 1~1 〇 # m. Makeup u_ ^ 又 Put this gentleman under appropriate conditions, for example, pre-bake 1~"A from 7 0~1 5 0 〇C, the main cloth is also minute thick ice from, ·, μ | u 丄jij Only > six θ 丄 ~ π eight after roasting, to know the defensive Α 1 υ continuation. You u measured at this stage;; the intensity of the exposure of the coating film, the measurement #pre-block, followed by the pre-:: 'referred to as the "film thickness before imaging" ° month to the unexposed part, will be residual , contact with a suitable developer to dissolve the image. Here, it is obvious. The exposure part is washed according to the necessity, and will be coated: 夕成儿α... The composition of the image agent and the conditions of the development, the system - Γ布仲": The composition of the moon 作 is suitable for selection. As the imaging, the ° match test = The unexposed part can be completely dissolved... Bu, which is insoluble under suitable conditions, for example, 2〇~=布骐 baking under 18〇~28〇t. After the post-baking, the system is coated. The thickness of the film is set to t clock, and the film thickness after hardening. "The final film thickness and the final hardening residual film rate measured according to this. The residual film rate (%) - (the film thickness after final hardening (pre-X 100 ν μιη)) Residual film rate; ~ In addition, the same curable resin composition is applied to the substrate to dry on the same conditions as in the enamel, and pre-baking step, sheep measurement: The reference coating film is used to make it complete Strong curing light: After J cloth, the film thickness was measured. The film thickness at this stage was set to "complete exposure: two first thick". After that, the exposed coating | g y % ^ * 朕 依 依 依 不 依 依 依 依 依 依

\\312\2d-code\90-04\8912]019.ptd Page 49 1260329 V. Description of invention (47) After baking after the event + it is "Film thickness after final hardening = Description: Method determination The film thickness 'is set to + 厗 厗 而 而 而 由 由 由 由 由 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全 完全(The final film thickness without the imaging step (^) + the full exposure film thickness (μπΟ) X 1〇〇 calculates the reference residual film rate. r = :T f calculates the residual film rate and the reference residual film rate, and the residual film rate is The minimum exposure amount with the same residual film rate is determined as the minimum exposure. The smaller the low exposure amount, the higher the sensitivity. 2 According to the present invention, the minimum exposure amount determined according to the present invention is i. 〇〇mj/ m' should be 5〇mj/cm2 or less 'preferably 35mj/cm2 ultra-high sensitivity hardenable resin composition. Reed Hi: more i匕ί resin composition 4Do not be suitable for color filter a column spacer for the color gap of the sheet, and a unit for maintaining the liquid crystal panel, ί ί ΐ a black matrix formed in a pattern on the transparent substrate, and a certain black matrix on the δ hai black matrix私# — .« ^ ^ , ^ The color layer formed by the 疋图木, and the protective film covering the y = π ^, there is also a case where the η = bright electrode is formed on the protective film. The black base layer is formed on the electrode plate or the colored layer or the protective layer to form a column spacer. The color layer is a red pattern, a green pattern and a blue pattern is a mosaic type, a strip type f-type The desired pattern of the four-dimensional configuration type is arranged, and the black-based system is disposed between the respective colored patterns and the colored layer forming region.

1260329

V. Description of invention (48) Fixed area. The colored layer can be formed by various methods to form a curable resin composition by a pigment dispersion method. Also, using the above-mentioned material in the above-mentioned curable resin composition, the surface of the two sides is coated, and the ultraviolet ray is irradiated through the reticle: second, after the image is heated and hardened by a clean electric furnace or the like, Color layer. The colored layer usually forms a red 5 or so and the 叮 shape = system can be formed by any method of dyeing, pigment dispersion, printing:: accumulation method, or chrome steaming /

The protective film can be formed into a transfer applicator, a light applicator, a spray coating, a printing or the like by a solution of the above-mentioned curable resin cloth: for example, it is formed to have a thickness of about 2 (four). In the use of rotation:: cry and ί number is set in the range of 500~1 500 rpm. Hardenability, 曰 = object discussion, by irradiating ultraviolet light through a mask. ^ 2: After alkali imaging, 'heating in a clean electric furnace to form a transparent electrode on the protective film, using indium tin oxide ( Ιτ〇), (, _, 匕, tin (Sn〇) and alloys of these substances are formed by a general method such as a spray method, a steaming symmetry method, or the like, and in addition, light can be used as necessary. The etching or the device of the resist forms a prescribed pattern. The thickness of the transparent electricity: can be set to about 20 to 50 nm, preferably about 1 to 3 〇〇 nm. The column spacer on the transparent electrode can also be used. The coating liquid of the hardened product is applied by a spin coater, a light coater, spraying, printing, or the like, and the photomask is used as a violet image, and then heated by a clean electric furnace or the like (4). Spacer =

1260329 V. Description of invention (49) Become the height of 5 / Z m. The number of revolutions of the spin coater is the same as that for forming the protective film, and should be set within the range of 50,000 to 15 rpm. An alignment film is formed on the inner surface side of the color filter manufactured in this manner, and is opposed to the electrode substrate, and the liquid crystal panel is obtained by filling the gap portion with liquid crystal and sealing it. [Examples] (Example 1) (Synthesis of high-sensitivity resin (1')) The following components were used:

• Benzyl methacrylate (BzMA): 2 50g • Styrene (St): 350g • Acrylic acid (AA): 200g • 2-Hydroxyethyl methacrylate (HEMA): 20 0 g of four compounds with azo 5 g of diisobutyronitrile (AIBN) was dissolved in 65 g of 3-methoxybutyl acetate, and the resulting solution was dropped into 3-methoxybutyl acetate at 6 ° C for 6 hours. In the polymerization tank of the ester i〇〇〇g, it is polymerized to obtain a solution of the base polymer. Next, in the obtained raw material polymer solution, the following composition was added at a time:

• 2-Methyl propylene oxirane ethyl acrylate (M〇I): 24 〇 g • Dibutyltin laurate: 1 g • 3-methoxy butyl acetate: 22 6 〇g • Total hydrogen (11 卩): 2.5 times the mixture is added once, heated and stirred to obtain the alcohol before treatment

89121019.ptd Page 52 1260329

The reaction solution of the sensitivity curable resin (1') was asked. The progress of the reaction was monitored by i r (infrared absorption spectrum) until the peak caused by the isocyanate group of 2 2 0 0 c m-1 disappeared. The device ratio (% by mole) of each monomer is as follows. Benzoyl phthalocyanine · stupid ethylene: acrylic acid: methyl methacrylate 2 hydroxyethyl ester: isocyanic acid 2-mercapto propylene oxyethylene vinegar II 13·3:31· 7:26· 2·· 14· 4 : 14· 4. Further, the equivalent ratio (NC〇/〇H) of the isocyanate group of 2-mercaptopropenyloxyethyl isocyanate to the hydroxyl group of 2-hydroxyethyl methacrylate is 丨·〇. The solid solution obtained by the eight solutions was divided into 25.5% and the viscosity was 7?·3 mPa·s/25 °C. After the obtained reaction liquid was applied onto a glass plate, the solvent was removed by drying under reduced pressure overnight at room temperature. The solid obtained had an acid value of 125.5 mgKOH/g and a weight average molecular weight of 4250. The various physical properties thereof were determined by the following methods. a·solid fraction: put the fine scale reaction liquid 〇· 7~〇·8g in the aluminum lol, dry it in a hot air dryer at 1〇5 C for 6~7 hours, then immediately weigh the dry weight to obtain the relative reaction liquid. The ratio of the dry weight of the weight. b. Viscosity (mPa. S/25 °C): A B-type viscometer was used, and the measurement was performed by using 牝1 at 60 rpm.

c. Acid value: The sample was dissolved in acetone, and the phenol red was used as an indicator to obtain a neutralization titration of 1 / 10 N NaOH. d. Hydroxy valence: The weight of K0H which can be obtained from the dry solid content of 1 g of the acetylated acid value. 'e · Weight average molecular weight: G P C measurement conditions and; j: Main column: Schodex GPC KF-805L (Showa Redding Baoshi No 冤工工)

1260329 'V. Description of invention (51) /7IL Yan · 1 · 〇 (m 1 / m i η.)

Temperature: 4 0 °C

Dissolved solution: tetrahydrofuran detector: RI (alcohol treatment of high-sensitizing resin (1,)) Amount of reaction liquid containing curable resin (1,) ((4) is divided into 2 5.5 weight 1 / butyl butyl ester solution), Add the 丨〇 weight% ratio to the side: "after" to make it ripe. The 90 C heating of the reaction solution added with ?-pentanol is used to disturb the old and seasonally mature. $Others will be the other ones. ° Force: stir it for 3 hours to make it ripe. In the case of the end of the ripening, the area ratio of the acid anhydride group 1:83, ~1 822 CW] / benzene ring [683 to 721 cn rl] m was confirmed by FT-IR spectroscopy to be less than or equal to 3. Thus, a reaction liquid of the alcohol-treated body t high-sensitivity-curable resin (1) containing the high-sensitivity-curable resin u,) was obtained. 5%。 The solids concentration of the obtained reaction liquid was 23. 2% by weight, the viscosity was 49. 5mPa · s / 25 °C. • 曱酴 曱酴 S acid varnish type epoxy resin (1) manufactured by SheU eP〇Xy Co., Ltd., Abby 180 180S70): 15.0 parts by weight • 2-methyl-1-(4-methylthiobenzene) Base) _2 morpholinoacetone - 丨 · · 2 · 1 part by weight.

• 2, 2'-bis(o-chlorophenyl)-4, 5, 4,5,-tetraphenyl-1,2'-diimidazole: 1. 5 parts by weight • diethylene glycol dioxime ether: 59.0 parts by weight of 3-methoxybutyl acetate: 7. 4 parts by weight was scrambled and mixed at a temperature to obtain a curable resin composition (1).

89121019.ptd Page 54 1260329

(Preparation of curable resin composition (丨)) Each of the following components: • The reaction liquid containing the above-mentioned high-sensitivity resin (1) (solid content: 23.2% by weight), 5 9 · 0 parts by weight • five Dipentaerythritol acrylate (manufactured by Saudi Arabia, SR3 9 9 ) · Parts · · U weight (Example 2) In addition to the charge ratio of each monomer, and the difference between the base of 2-hydroxyethyl acrylate Isocyanate-based deacetylation of 2-methylpropenyloxyethyl cyanate

The resin composition, the alcohol treatment, and the composition were prepared in the same manner as in the following examples, and the curable resin composition (2) containing the high-sensitivity curable resin σ (2 ) was obtained.曰 • BzMArSt: AA: HEMA: M0I- 1 2. 9 : 25. 6 : 25. 3:1 6.4 : 1 9. 7 • NC0/0H=1.2 ' (Example 3)

The ratio of the charge ratio of each monomer and the equivalent ratio of the isocyanate group of 2-methylmercaptopropenyloxyethyl isocyanate to the methyl methacrylate 2 The synthesis of the resin, the alcohol treatment, and the preparation of the composition were carried out in the same manner as in Example , to obtain a curable resin composition (3) containing the high-sensitivity curable resin (3). 'BzMAiStiAAiHEMAiMOI^^. 3:24. 4:24. 1:15 7β23 5 • NC0/0H=1. 5 (Example 4)

In addition to the polymerization initiator used to prepare the base polymer, from 5 g of A I B N

1260329

(Nitrile) changed to the same amount of 2, 2, - azobis (2, A, (non-nitrile), and will make isocyanate " propylene oxyethylene: J, since 2. 5 g of hydrogen (10) was changed to the same amount of 3, : other than diphenyl hydroxytoluene (10) T), in the same manner as in Example 1, the synthesis of the resin, the alcohol treatment, and the preparation of the composition were carried out to obtain a second resin ( 4) A curable resin composition (4). (3) A feeling of sensation (Example 5) A methacrylic acid oxime obtained by containing a high-quality resin in addition to the reaction of the isocyanic acid in the solution of the raw material polymer, in the same manner as in Example 4 (5) A curable resin composition (5). (Example 6) In addition to the charge ratio of each monomer, and the isocyanate group of 2-methylpropenyloxyethyl isocyanate of 2-hydroxy group by hydroxyl group, the change was as follows. The composition of the resin field, the alcohol treatment, and the composition are prepared in the same manner as in the above, and the curable resin composition (6) containing the high-sensitivity hardening port (6) is obtained.曰• BzMA: St:AA:HEMA:MO1 = 0:35. 7:2 4. 0 :1 8. 3 : 2 1 9 • NC0/0H=1. 2 ' (Example 7) except in the base polymer In the solution, the hardening resin composition (7) containing the high-sensitivity resin (7) was obtained in the same manner as in Example 6 except that the reaction was carried out by dropping 2-methylpropenyl ethoxide in isocyanate. (Example 8) In addition to the charge ratio of each monomer, and 2-hydroxyethyl acrylate

89121019.ptd Page 56 1260329 ___ V. OBJECTS OF THE INVENTION (54) The equivalent ratio of the isocyanate group of 2-hydroxycarbonyl isocyanate of hydroxy isocyanate is changed in the following manner, in the same manner as in Example 1. The synthesis of the resin, the alcohol treatment, and the preparation of the composition are carried out to obtain a curable resin composition (8) containing the high-sensitivity curable resin (8). • BzMA: St : AA : HEMA: MO 1-0: 38. 2:21. 2:18·5:22·2 • NC0/0H=1.2 (Example 9)

A curable resin composition containing a high-sensitivity resin (9) was obtained in the same manner as in Example 8 except that the reaction was carried out by dropwise addition of 2-methylpropenyloxyacetate to the solution of the base polymer. (9 ). (Example 10) In addition to the polymerization initiator which will modulate the base polymer, 2, 2'-azobis(2-mercaptopropionic acid) dioxime is further converted from 5giAIBN (monthly system). The ester (Π 'human non-nitrile), and the isocyanate 2-methyl propyl oxime oxyethylene ® reaction 2, / i inhibitor, from 2. 5g hydrogen brewing * (HQ) changed to the same amount 3, 5_2 f 2 I 4~hydroxytoluene (BHT), and in addition to the solution of the isocyanate 2-mercaptopropene oxyhydroxide polymer, (iv) obtained in the second embodiment of Example 6, Curable resin group containing high sensitivity resin (10)

(Embodiment 1 1)

a polymerization initiator for the preparation of a raw material polymer, from 5 g of BN (dImP5 and $2, 2'-azobis(2-mercaptopropionic acid) dioxime) The isocyanate 2-mercaptopropene oxime ethyl ester will be reacted with water 0 卬 preparation, and changed from 2·5g of nitrogen hydrazine (HQ) to the same amount of 3, 5 - 2

89121019.ptd Page 57 1260329 V. INSTRUCTIONS (55) Third butyl 4-hydroxyindole benzene (BHT), and 2-oxiranyl propylene oxyethyl isocyanate is dropped into the solution of the base polymer The synthesis of the resin, the alcohol treatment, and the preparation of the composition were carried out in the same manner as in Example 1 to obtain a curable resin composition (1 1 ) containing the high-sensitivity resin (1 1 ). (Example 1 2) (Preparation of photocurable resin composition (1 2 ) and (1 2,)) Each of the following components: • A reaction liquid containing the high-sensitivity resin obtained in Example 1 (solid content) 23· 2 wt%) : 97. 0 parts by weight

• Pentaerythritol pentaacetate (manufactured by Saudi Arabia, SR3 9 9 ) : 1 8 · 〇 by weight • 曱 曱 acid varnish type epoxy resin (oiled by SheU epoxy, Abby 180 180S70) : 2·0 parts by weight • 2-mercapto-2-N,N-dimethylamino-b (4-morpholinophenylbutanone: 2 · 5 parts by weight • 2, 2 - two (neighbor) Phenyl 4,5,4,5,4-tetraphenyl-,-diazole: 2. 〇 parts by weight of polyoxyethylene octyl phenyl ether (nonionic surfactant HS_21 〇, manufactured by Sakamoto Oil Co., Ltd.) :3 · 6 parts by weight

• == alcohol-methyl ether acetate: 59·〇 parts by weight The mixture was stirred and mixed under a coffee to obtain a photocurable resin composition (1 2). , :r, in place of the reaction containing the high-sensitivity resin (1) in the above composition, only the high-sensitivity resin (1, ) liquid containing the alcohol-free treatment obtained in Example 1 was used to obtain a photocurable resin. Composition (丨2,).

Page 58 1260329 V. INSTRUCTION OF THE INVENTION (56) (Storage test) The viscosity of the photocurable resin composition U 2) and the photocurable resin composition (1 2 ) was measured by a B-type viscosity meter immediately after preparation. 5mPa。 s / 25 ° C. The photocurable resin composition (12,) was measured to be 20. OmPa · s / 25, the alcohol-treated photocurable resin composition 〇 2) was i8. 5 mPa. s / 25 ° C. (Example 1 3) (Formation of a black matrix) On a glass substrate (AL material manufactured by Asahi Glass Co., Ltd.) having a thickness of 1 mm, the following components were mixed: Black pigment: 23 parts by weight of a south molecular dispersant: (Bic Chemi Disperbyk 111 manufactured by Japan Co., Ltd.: 2 parts by weight of a dying agent (diethylene glycol dioxime ether): 75 parts by weight of a component 'dispersed in a sand mill to prepare a black pigment dispersion. Next, the following components are used: The above black pigment dispersion liquid··6 1 part by weight of the curable resin composition of Example 1 (i: 2 parts by weight • diglyme: 30 parts by weight) The mixture was mixed to obtain a composition for a light-shielding layer. Next, a glass substrate having a thickness of 1 · 1 mm (AL material manufactured by Asahi Glass Co., Ltd.) was applied, and the composition for the light-shielding layer was applied by a spin coater to dry at 1 〇〇 t: ^ 3 minutes, a light-shielding layer having a film thickness of about 1 Am is formed. After exposing the light-shielding layer to a light-shielding pattern with a super-high mercury lamp, the substrate is k ' 〇 % 5 % hydroxy 彳 b potassium solution, and then the substrate is further Place 30 minutes in the atmosphere of 丨8 〇〇c

89121〇19.ptd Page 59 1260329 V. INSTRUCTIONS (57) In the heat treatment, a black matrix is formed in a region where the light shielding portion should be formed. (Formation of colored layer) ^ On the substrate on which the black substrate was formed as described above, a red curable resin composition of the following composition was applied by a spin coating method (after coating, the crucible was dried in an electric furnace at 70 t for 30 minutes. Then, from the coating film of the red curable resin composition, the photomask is placed at a distance of m, and the ultraviolet ray lamp is used to approach the aligner, and the ultraviolet light is irradiated only in the region corresponding to the formation region of the colored layer.丨0 sec. Then, it was immersed in a 0. 0 5 % potassium hydroxide aqueous solution (liquid temperature 2 3) for 1 minute, and the uncured portion of the coating film which only removed the red curable resin composition was examined. Then, by placing the substrate in a 丨8 〇 〇 atmosphere for 3 施 minutes for heat treatment, and forming a red floating pattern in the area where red 昼 应 should be formed. Second, use the following composition of green The curable resin composition is formed in the same manner as the red floating pattern, and a green floating pattern is formed in a region where green halogen is to be formed. Then, a blue curable resin having the following composition is used. The object, according to the red ocean, the same step of pattern formation, forms a floating pattern of the color in the area where the blue pixel should be formed. Thus, it is made of red (foot), green (G), blue ( B) The coloring layer consisting of three colors: a. Composition of red curable resin composition • C · I · Pigment red 17 7 : 1 〇 by weight • Polyacid type polymer dispersant: 3 parts by weight. The curable resin composition of Example 1 (〗 〖) 5 parts by weight 89121019.ptd Page 60 V. Description of the invention (58) • 3-methoxybutyric acid acetate: composition of 82 parts by weight of the color-curable resin composition • 1 · Pigment Green 3 6 : 1 〇 Weight by weight dispersion 'Weights = Curing resin of Example 1 · Acetic acid 3-methoxybutyl vinegar: 82 parts by weight). Composition of 5 heavy-duty pot color hardening resin composition • L·I·Pigment Blue: 10 parts by weight. 2 sulfonic acid type polymer dispersant: 3 parts by weight.: The curable resin group of Example 1 ^ acetic acid 3-methoxy butyl: 82 parts by weight. 5 cc. Injury (Example 14) (Coating of the curable resin composition (1)), Example i was dried, and the coloring was formed in Example 13. The resin composition (1) of the layer of glass was spin-coated: a coating film having a coating thickness of 2 //m. (Formation of Protective Film) The coating film of the chemical resin composition (1) was placed at 1 Torr. (4) The distance between the cover and the close aligner is 2· 〇 kW ultra-high pressure mercury lamp, and the ultraviolet ray is irradiated for a second time in the area where the coloring is formed. Then, the target was immersed in a 05% potassium hydroxide aqueous solution (liquid temperature 23 < t) for 1 minute in the image, and only the coating film of the curable resin composition was removed, and the substrate was placed at 20 0. Place the 彳 彳 knife for 30 minutes in the atmosphere of °C. And a protective film is formed to obtain the color filter of the present invention. σ..., 1260329 5. Inventive Note (59) (Example 1 5) (Coating of Photocurable Resin Composition (12)) On a glass substrate in which a colored layer is formed, it will be paid and paid The petrochemical resin composition (12) was dried by a spin coating method as in Example 1 to form a coating film having a thickness of 5 (four). ^Re-formed old cloth, (formation of spacer) U-coated resin composition (1)) coating film, in the shape of 〇〇 ΐ ' 'large, size and spacing exposure pattern and set to 3,, light Cover, close to the aligner using 2 〇kw ultra-high pressure water% exposure =, the spacer on the color substrate forms the area to illuminate the ultraviolet 丨〇 second shovel % lamp only _ ΐ〇. 〇 σ 5% potassium oxide aqueous solution (liquid temperature Immerse 1 point in 23°c). Then, in the image-removing resin composition, only the photo-curable resin composition is removed, and the color filter of the present invention is obtained by processing the substrate in a subsequent atmosphere to form a spacer.里也Μ Q Example 1 6 ) ^ See Example 1 5 for the color filter with a fixed spacer plate temperature of 200 t; using argon and oxygen as the discharge gas, according to the sink magnetron The second method uses 1 τ 〇 as the standard dry to form a transparent electrode film. Then, an alignment film composed of polyimine is formed on the through film. [7] The above-mentioned color filter and the glass substrate on which the TFT is formed are made of a ring-shaped cream as a sealing material, and under a pressure of 3 kg/cm2, a constituent unit is bonded under the pressure of 150 kg, and sealed with a liquid crystal. Liquid crystal display device of the present invention (Embodiment 1 7) 89l2l〇i9. Page 62 1260329

After the DC magnetron is applied to the real film or the solid film, it is composed of the second resin. Example 1 3 Example 1 4, the base tube is sprayed on the transparent layer, and the upper layer is used as a dense σ — early 兀, = on the colored layer of the glass substrate having the colored layer, / is colored layer and protected The reverse glass of the film is made of argon and oxygen as a discharge gas, and a transparent electrode film is formed by using I τ 依法 as a standard. On the electrode film, an alignment film composed of a polyimine was formed in the same manner as in the procedure of Example 5 to obtain a color filter. The color filter and the glass substrate on which TF τ was formed were bonded by a pressure-sealing material of 3 kg/cm 2 at a pressure of 1 50 c and sealed with TN liquid crystal to prepare a GH-NMR analysis of the liquid crystal display device of the present invention. 5 g of the reaction liquid containing the alcohol-treated high-sensitivity resin (1) obtained in Example 1 (solid content of 2 3 · 2% by weight of 3-methoxypropenyl acetate solution) was diluted with 5 g of tetrahydrofuran. Stir in a 30 Og of isopropanol and drip in small amounts on a small amount. Thereafter, the supernatant was discarded, and the solid portion solidified at the bottom surface was completely dissolved in 5 g of tetrahydrofuran, and then dropped into 3 〇〇g of isopropyl alcohol. The obtained solid fraction was completely dissolved in 2 g of tetrahydrofuran, and similarly dropped into 300 g of hexane. The precipitated solid was filtered, and dried under reduced pressure at room temperature overnight to prepare a sample. The sample obtained had an average molecular weight of 94,000. This sample was completely dissolved in the weight]m〇, and the results of Μ-NMR analysis were as follows. ^-NMRCDMSO-d) σ Ppm σ 0·2 〜1 · 1 (m,12Η) σ 1· 1 〜1· 8 (m,19Η)

1260329 V. INSTRUCTIONS (61) σ 1. 85 α 3. 2 7 σ 3. 51 σ 3 . 9 0 σ 4. 08 σ 4. 75 σ 4. 90 σ 5. 6 3 σ 6. 0 5 σ 7 11 σ 7· 31 σ 12. 04 (s, (b, (b, (b, (b, (b, (b, 3H) 2H) 2H) 2H) 2H) 1H) 2H) (s, 1H) (s, 1H) . (b, 23H) (b, 6H) (b, 2H) The unit of each constituent unit in the high-sensitivity resin (1) which has been subjected to reprecipitation purification by 1H-NMR angle analysis Ratio (Morby), benzyl methacrylate B: propyl phthalic acid: methyl ^, knee lack 9 -, ~ 7 ^ fine 酉 2 - acetonitrile day: isocyanate 2-methacryl oxime Oxyethyl ester = 2 : 5 : 4 : 2 · 1. Also, α 纽 ethoxy brewing (the MOD's lead (mole) is 8 cyanine 23 cyanate 2-methyl propylene (2) according to the same method, will contain other implementations, ear / a) The reaction solution of ~(1 1 ) was reprecipitated and purified, and the result in the first table of the sensitization resin I was analyzed by H1 NMR as a result of the sensitivity evaluation described later. Analysis (Evaluation of Sensitivity) / On the glass substrate of 10 cm, the resin composition (1) was applied by a spin coater (hardened form 1H-DX2 obtained in MUasa Example 1).

89121019.ptd Page 64 1260329 V. INSTRUCTIONS (62): Drying to form a coating film having a dry film thickness of 2 _ at 90 T; heating for 3 minutes. After heating, the J-alignment of the super-high pressure mercury lamp equipped with a 2.0 kW self-coating (from the arranging mask) is made up of the same coating film (manufactured by Dainippon Printing Co., Ltd., Form MA 12〇〇). The area is irradiated with ultraviolet (five)/cm in intensity of 25, 35, 50, innmi/?, illuminance (405-, after ultraviolet irradiation, the coating of the giant part is removed from the four areas) Partially exposed, the measuring device (Dektak 1 60 0, manufactured by Abu Dhabi Co., Ltd.) ^^ 膜 the film thickness of each ray-inducing region as the film thickness before development. Next, at the exposure portion of the coating film, Rotating the developing machine (A叩1 ied Process Techn〇1〇gy, INK, M0DEL: 915), 5% 5% by weight of aqueous solution of hydrazine and potassium hydroxide was dissolved for 60 seconds to dissolve and remove the unexposed part, and the residual exposure was observed. The pure water was washed with water for 6 sec. After the image was developed, the "2\nV"' electric furnace of the exposure unit (SCOV-250 Hy-s0, manufactured by the Institute of Tobacco Research) was heated in the guanamine plant for 0 minutes. Finally, the f-thickness of each region of the obtained film is measured by the above method as the final hardening. Thickness before imaging to measure the film thickness after curing and finally, the residual film rate is calculated according to the following equation. Sub partner

The film thickness after the residual film rate hardening (film thickness before development (#m)):: square Φ, the reference residual film rate is determined in the following manner. First, the film is completely exposed to the intensity of W100mJ/cm2, and the method of the sample is the same as that of the sample. (4) The hardening resin composition (1) is completely

89121019.ptd 1260329 V. Description of invention (63) Thick. Next, the surface is coated with 100mJ/cm2. The light is applied to the sample according to the method of the sample, and the method is used to measure the image without the imaging method as the non-developing step; the exposure film thickness and the non-development step are as follows. The most embarrassing ',:. The complete rate since the determination. , , ,; film exhaust, according to the following formula to calculate the reference residual film reference residual film rate (%) = (no imaging step film thickness) two sons (heart) + complete exposure will be calculated according to the residual film rate The minimum exposure amount is equal to the minimum exposure amount of the inner dry film and the reference residual film rate. The mountain is determined to be the hardening resin composition (1) and the same as the above method, - the resin composition (2) ~ ui} t / ς成 /, his application of the hardening of the final hardening after the film thickness / film coating / film, measuring the thickness of the wood film, and the benefits of silly boat thick as: set each hardening resin composition (7) ~(1), for each curable resin composition (~ light amount. The result is shown in the first table. 疋取低低1260329 V. Invention description (64) [Table 1] Table 1 (1/2) Composition ratio BzMA: St:AA:HEMA:M01 NCO /OH recombination initiator / recombination inhibitor drop is > \ N \ high sensitivity resin / hardenable resin composition (1) 13.3:31.7:26.2:14: 4 1.0 AIBN/HQ M ^ \ w High-sensitivity resin/curable resin composition (2) 12.9:25.6:25.3:16.4:19.7 1.2 AIBN/HQ to high-sensitivity resin/curable resin composition (3) 1 2.3:24.4:24.1:15.7:23.5 1.5 AIBN/HQ High-sensitivity resin/curable resin composition (4) 13.3:31.7:26.2:14:4 1.0 DAMP/BHT fte y \ \ \ High-sensitivity resin/curable resin Composition (5) 13.3:31.7:26.2:14:4 1.0 DAMP/BHT Drop-in high-sensitivity resin/curable resin composition (6) 0:35.7:24.0:18.3:21.9 1.2 AIBN/HQ j \ \ \ Sensitivity resin composition resin composition (7) 0:35.7:24.0:18.3:21.9 1.2 AIBN/HQ Drop-in high-sensitivity resin/curable resin composition (8) 0:38.2:21.2:18.5:22.2 1.2 AIBN/ HQ te High sensitivity resin/curable resin composition (9) 0:38.2:21.2:18.5:22.2 1.2 AIBN/HQ Drop high sensitivity resin/curable resin composition (10) 0:35.7:24.0:18.3:21.9 1.2 DAMP/BHT Drop-in high-sensitivity resin/curable resin composition (11) 0:38.2:21.2:18.5:22.2 1.2 DAMP/BHT Drop in 89121019.ptd Page 67 1260329 V. Description of invention (65) Table 1 (2/2) ih-nmr (mole) Minimum hardening exposure (mJ) High-sensitivity resin/curable resin composition (1) 8.02 100 High-sensitivity resin/curable resin composition (2) 12.0 50 High-sensitivity resin /curable resin composition (3) 16.0 35 High-sensitivity resin cis-resin composition (4) 8.07 50 High-sensitivity resin cis-resin composition (5) 8.05 50 High-sensitivity resin cis-resin composition (6) 18.7 50 High-sensitivity resin / Curable resin composition (7) 19.5 35 High-sensitivity resin/curable resin composition (8) 19.5 50 High-sensitivity resin/curable resin composition (9) 20.3 35 High-sensitivity resin/5-reducing resin composition (10) 18.7 35 High-sensitivity resin cis-resin composition (11) 20.7 25 llllill 89121019.ptd Page 68 1260329 V. Description of invention (66) (Evaluation of preservability) The unobtained product obtained in Example 1舻♦ wk 4 — The reaction liquid of the high-sensitivity resin (1 ') treated with the G-spot, the s-G, the s-, and the S-sub-process, and the 鬲 containing the alcohol-treated, Λ, 人, and η ^ ^ The reaction liquid of the sensitivity resin (1) is kept in the 彳I t P at cold, room temperature and high temperature. Then, the storage period is measured by a B-type viscometer. H is carried out immediately after the whole week, so that the product (1 2 will be) is obtained by the extensive example j 2 , the alcohol-treated curable resin group Β ^ ° ^ ^ ^ ^ ^ ^ T ^ I. ^ The ratio of the point immediately after the modulation is adjusted, the viscosity of the #干干于楚9生的存期 is the same as that of the second table and the third table. [Table 3] Cold storage (2 weeks) to temperature Preservation (2 weeks) (70. 〇, Γ 曰 2nd table r^ Sensitivity resin (1) (alcohol treatment) ^ Ι.ΤοΤ^ΓTToYoli High sensitivity resin (1 (untreated 01 1 times 172 times 1 · 5 0 0 Times 1260329

89l2l019.ptd Page 70 1260329 Table 4, Invention Description (68) [Table 5] -^---- Composition Specific Gravity Initiator / Recombination Inhibitor Instillation 3 6 Onm 4 0 0 nm 4 8 5nm high sensitivity resin (1) same AIBN/HQ benefit 2 4 (%) 64 (%) 6 6 (%) high sensitivity resin (4) DAMP/BHT benefit 70 87 1 94 high sensitivity resin (5) DAMP/BHT drop 3 3 73 90 [Effect of the invention] - as described above, the street % π corpse; the 桅 桅 supply, the 鈥 degree hardening resin, the 苴 molecular structure is composed of at least a constituent unit having an acidic functional group, The main chain composed of the constituent units of the hydroxyl group is composed of a compound containing a radical and a compound of isocyanic acid, and the isocyanate g group is less than the above-mentioned acidic group; And/or combined with the above hydroxyl group to the aminocarboxylic acid I, and containing a radical polym. The amount of ^_ as the ester compound is converted into the equivalent ratio of the relative main chain - the equivalent ratio of the acid (NC0/0H), which is adjusted to be the main component of the phthalate-based sensitivity hardening resin. The structure of the chain and the side chain is more preferably: high: the amount of charge having a constituent unit of the base is adjusted: 14:: the amount is a base polymerizable group, 35 degrees is very high, and can be less than two Free hardening. Exposure is placed in a short time.

1260329 V. Inventive Note (69) - Further, the high-sensitivity hardening resin of the present invention can be subjected to alcohol treatment as necessary. Even if it is dissolved or dispersed in a solvent, such a drunk treatment body is less likely to cause an increase in molecular weight or an increase in viscosity, and the car is not treated with an alcohol-treated body, and the stability is extremely high. Therefore, the storage property is excellent when prepared into a solution, and can be stored for a long time... The solution of the alcohol treatment body does not have a viscosity during use: it is easy to handle. Further, in the production of the high-sensitivity curable resin of the present invention, a raw material polymer is prepared by preparing a non-nitrile azo-based or peroxide-based polymerization initiator, and/or a compound selected from the above formula (8) or formula (15) is used. The polymerization inhibitor of the compound shown is introduced into a radical polymerizable group-containing isocyanate compound, and a curable resin excellent in availability is not preferable. Also, in the case of high transparency, photosynthetic

The portion reaches the inside of the curable resin coating film and provides a measure of sensitivity. The shell of the photocurable resin containing the curable resin as the main component is sensitive to the south and can be hardened in a short time with a small amount of exposure. The curable resin composition of the present invention is less likely to cause an increase in viscosity, and has a high storage property and a coating film and pattern which are not uniform in coating. Further, it is known that the curable resin composition is required to have a high i. · The door edge Θ "sheng ^ can also make the hardening of the invention

^^ w The peripheral layer is used as a coloring layer for the color filter, a protective layer covering the colored layer, and a photoresist material for maintaining the column spacer of the panel. That is, the curable resin composition of the invention, which is high in sensitivity, is productive for use;

Excellent coating properties, uniform formation and excellent dimensional stability: 丄E ”

89121019.ptd

1260329 V. INSTRUCTIONS (70) Layers, protective films and column spacers, and satisfying the requirements for transparency of the colored layer and the protective film. [Description of component number] 1 color filter 2 electrode substrate 3 gap portion 4 sealing material 5 'transparent substrate 6 color base layer 7 (7R, 7G, 7B) colored layer 8 protective film 9. transparent electrode film 10 11 beads 12 column spacers

89121019.ptd Page 73 1260329 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a liquid crystal panel. 2 is a schematic cross-sectional view showing another example of a liquid crystal panel.

89121019.ptd第74页

Claims (1)

1260329 Case No. 89121 (119 牴 4· Sixth, the scope of application for patents &gt; 1 · A high-sensitivity hardening resin, 苴 辨 + +, ^ VL kiL from ^ has at least an acidic functional group of the structure of a single W, l &lt; 7 tree wall system The main chain is composed of a compound containing an ethyl group, and the part of the compound is used as a guanamine bond and/or combined with the above-mentioned base group and s C-based formic acid vinegar. The above-mentioned:, the amount of the isocyanate compound of the earth-water five-group is converted to the equivalent ratio (NC0/0H) of the above isocyanate group to the base of the main chain, which is 1 · 2 Above, 2 · 〇 below. The high-sensitivity-curable resin according to the first aspect of the invention, wherein the constituent unit having the hydroxyl group is based on the total amount of each constituent unit constituting the main chain and the side chain of the high-sensitivity resin. The amount of charge is more than % by mole. ' 3. The high-sensitivity-curable resin according to the second aspect of the invention, wherein the constituent unit having the acidic functional group is based on the total enthalpy of each of the constituent units constituting the main chain and the side chain of the high-sensitivity resin. The charge amount is 1 〇 to 30% by mole, the charge amount of the constituent unit having the hydroxyl group is 14% by mole or more, and the charge amount of the above-mentioned radical polymerizable group isocyanate compound is 14 More than 5% by mole, the acid value is 80 to 14 〇 mg K 〇 H / g, and the weight average molecular weight in terms of polystyrene is 10,000 to 1 Torr. 4. The high-sensitivity hardening resin according to the third aspect of the invention, wherein the constituent unit having the acidic functional group is based on the entire constituent units of the main chain and the side chain constituting the high-sensitivity resin. The charge amount is 10 to 30 mol%, and the above-mentioned charge amount of the constituent unit having a hydroxyl group is 1260329 --- 6. The patent application range is 15~19 mol%. The loading amount of the material is polystyrene. 5. A high-sensitivity consists of at least one part of the energy base composed of a compound composed of at least a unit. In the case of 1 Η-NMR measurement of the constituent monoester compound of the amino group as the main component, the main chain system is at least a constituent unit of the formula (2), and the above-mentioned radical polymerizable group-containing isocyanate is compounded at 18 ～26 mol%, the acid value is 90-120 mgKOH/g, and the converted weight average molecular weight is 3 0 0 0 0~6 0 0 0 0. The curable resin is characterized in that the curable resin has a constituent unit of an acidic functional group and a main chain having a hydroxyl group, and the isocyanate group of the isocyanate isocyanate compound containing a radical polymerizable group is as described above. The acidic moiety is composed of a combination of a guanamine and/or a combination of at least a formate of the above hydroxyl group; The above-mentioned radical-introducing group containing a radical polymerizable group is introduced, and after removing a component having a molecular weight of 5 Å, milk, or 5 Å or less in a range of 8 mil or more, a high-sensitivity resin having a sensitivity of 2 or 5 is used. ^ The constituent unit shown by the following formula (1) is the following formula (1); the formula (1) RI - (CH2-C) - I c = o I OH RI - (CH2-C) - I c = o I 〇 OH 1260329 _____ Case No. 89112019_ Amendment of the date of the year 6. Apply for the general outline &quot;^ &quot;&quot; ' --- (In each formula, R is hydrogen or carbon number 丨~5 alkyl, R1 table carbon number 2 ~4 alkyl). 7. A high-sensitivity hardening resin according to claim </RTI> or claim 5, wherein at least a portion of the acidic functional group of the main chain in the pot has an alcohol intercalated with a hydroxy &amp; ester. </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The compound containing a double bond group and a hydroxyl group is formed by polymerization using a non-monthly azo polymerization initiator or a peroxide agent. 9. The high-sensitivity hardening resin according to the ninth or fifth aspect of the invention, wherein the oxime radical polymerizable group isocyanate compound is a phenol compound selected from the following formula (9) and the following formula (15) The polymerization inhibitor of the phosphite-based compound shown is introduced into the main chain portion of the above-mentioned high-sensitivity hardening resin: Formula (9) 〇Η V^R9 R6 (wherein R6 represents hydrogen, carbon number is 1 to 5) Burning base, or the following formula (l〇) · formula (10) * 1260329 -__Case No. 89112019 _Yearly Month Day Amendment VI, Application Paste® ~ 'Form D in Table (10) - S-, carbon number 1~1 伸 alkyl or carbon number 1~ 1 0 Burning fork base; R7 table carbon number i ~ 丨〇 alkyl; RS hydrogen, carbon number 1 _ ~ 10 alkyl, or the following formula (11): stomach ^ (11) R in the formula (11), G, carbon number 1 to 丨 0 alkyl or carbon number i ~ oxime alkylidene; R9 hydrogen or carbon number 1 ~ 1 〇 alkyl; only! ^7 And at least one of them is a tertiary butyl group or an alkyl group having a cyclohexyl group; further, the substituents of the same symbol may be the same or different) Formula (15) Rn (In the formula, 'R11 is hydrogen or carbon number 1~2〇). 1 0. The high-sensitivity hardening resin according to item 8 of the patent application, wherein the solution of the acetic acid _3_decyloxybutyl ester as a resin solid content is placed in a 1 cm-divided quartz cell, The light transmittance under 4〇〇ηπ1 is 6〇% or more. 匕\总档\89\89121019\89121019(replacement)-l.ptc Page 78 j26〇329 Revised Yueshou Case No. 89112019 VI. Patent Application Area 11. High-sensitivity hardening resin according to item 8 of the patent application scope The straight H resin is divided into 20% by weight of acetic acid _3 monomethoxy butyl brewing solution placed in the above S-point stone cell slot, the light transmittance at 36 〇 nm is 50 〇 / 〇 12 A method for producing a high-sensitivity curable resin, comprising: a raw material polymer having a main chain composed of at least an acidic functional group and a hydroxyl group; The compound is a rat acid, and the compound 'is converted to an isochloric acid-alumina relative to the radical of the above main chain; and the S ratio (NCO/OH) is reacted at a ratio of 1.0 or more. 3 · High-sensitivity hardening according to item 12 of the patent application, which is the combination of the above-mentioned radical-polymerizable isocyanate acetylation: shoulder = ΐ ί to the above equivalent ratio (NC0/0H) to 1.2 What is the above ratio and the above principle? Compound reaction. 14. The method for producing a high-sensitivity hardening resin according to claim 12, wherein the equivalent ratio (NCO/OH) is 2 or less. 15. In the manufacture of the high-sensitivity-curable resin of claim 12, the above-mentioned components including the constituent units of the base are based on the total amount of the main chain and the side chain constituting the high-sensitivity-curable resin.枓 is more than 1 4 mol%. 16. The manufacture of a high-sensitivity hardening resin according to the fifteenth aspect of the patent application.::f is an acid functional group based on the core of the main chain and the side chain constituting the high-sensitivity curable resin. The basis weight of the constituent material is 10 to 30 mol%, and the fabric having the hydroxyl group is 14 mol% or more in summer, and the above-mentioned radical polymerizable group-containing odor acid 41260329 ' -_ Case No. 8912101Q_Year $ Day VI. Patent Application 酉曰 The loading amount of 酉曰 compound is 丨4 mol% or more. 17 . The manufacturing of the high-sensitivity hardening resin of the sixth paragraph of the patent application is based on the main chain and the side chain of the above-mentioned enamel-sensitive resin. The composition of the base material is 10 Γ 30 mol%, and the above-mentioned 具备:::f15~19 mol% of the constituent unit of the hydroxyl group, the above-mentioned radical-polymerizable group-containing isocyanate-曰匕δ substance The charge amount is 18 to 26 mol%. Manufacture of a high-sensitivity hardening resin according to item 12 of the patent scope of the patent application. The main chain of the middle name is at least a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (2). Composition: Formula (1) Correction % - (CH 2 - C) - c = o I OH Formula (2) I - (CH2-C) Ic = oI 〇 OH (each grapefruit VV, R table nitrogen or carbon number 1 to 5 A base group having a carbon number of 2 to 4 on the R1 group. 19. A method of applying a high-sensitivity hardening resin according to item 2 of the patent application, wherein the raw material polymer is dissolved or dispersed in a solvent to form a t ΛϊΙ 89121Q1A 1260329 - In the patent application _ into the t ί, the above-mentioned radical polymerizable group-containing isoleate compound cage 7 is reacted. The product of the high-intensity-hardening resin of the patent application range No. 12 is produced by the above-mentioned radical-containing polymerizable isocyanate-reducing human 4 2 1 , Thereafter, the alcohol is reacted with the base polymer. Go to · For example, the high-sensitivity hardening resin of the second paragraph of the patent application scope is manufactured with a compound containing a double bond group and an acidic functional group, and a peroxy sulfhydryl group and a base group. The compound 'is polymerized with a non-suspecting azo polymerization initiator or a polymerization initiator, and the above-mentioned base polymer is prepared, and the isocyanate compound of the radical polymerizable group is prepared. The production of a high-sensitivity hardening resin according to the first and second aspects of the patent application is carried out in the case of using a phenolic compound selected from the following formula (9) and the following: Under the polymerization inhibitor of the phosphite-based compound, the above-mentioned = radical polymerizable group isocyanate compound and the above-mentioned base polymer trans (9) 0H (wherein R6 represents hydrogen, an alkyl group having a carbon number of 1 to 5 or the following formula (1〇): 1260329 Case No. 89121019 修正 Amendment VI. Scope of Application for Patent (10) , D in the formula (10) -S-, an alkyl group having a carbon number of 1 to 10, or an alkylidene group having a carbon number of 1 to 10; an alkyl group having a carbon number of 1 to 10 on the R7; , an alkyl group having a carbon number of 1 to 10, or the following formula (11): formula (m OH R9 R6 t R8 R1G in the formula (11), carbon number 1 to 1 0 alkyl or carbon number 1 to 10 alkyl group; R9 hydrogen or carbon number 1 to 10 alkyl; And at least one of R8 is a tertiary butyl group or an alkyl group having a cyclohexyl group; further, the substituents of the same symbol may be the same or different) Formula (15) R11 (wherein R11 represents hydrogen or an alkyl group having 1 to 20 carbon atoms). 2 3. Manufacture of high-sensitivity hardening resin according to item 21 of the patent application scope C:\Total file\89\89121019\89121019 (replace)-1 .ptc Page 82 1260329 In the method, the solution of the acetic acid 3-methoxyl ester which is divided into 2% by weight of the resin is placed in the quartz cell defined by the icm, and the light transmittance at 4 〇〇 nm is 60% or more. . 24. The method for producing a high-sensitivity hardening resin according to claim 21, wherein a solution of the acetic acid-3-methoxyl ester as a resin solid content of 20% by weight is placed in an quartz cell of an icm division The light at 36 〇nm has a transmittance of more than 50%. A curable resin composition comprising a high-sensitivity curable resin according to item 1 or 5 of the above-mentioned patent application range as an essential component. In the case of the curable resin composition of the 25th article of the patent application, the film thickness of the pre-bright film is measured after exposure of the film formed by prebaking on the coated substrate of the bean. ), and the exposed film is imaged for post-baking and then measured for film thickness (after final hardening of the film), according to the following formula: residual film rate (%) = (final film thickness after hardening (before imaging) Membrane X 100 is used to determine the residual film ratio; D:: the if phase of the strain: the curable resin composition, "the same as the residual film rate, the conditions are applied to the substrate, and the pre-baked coating film is completely filmed by exposure. The film thickness (completely exposed film thickness) is determined, and the exposed coating film is measured under the nominal image forming step to determine the film thickness after the residue is cured (the film is finally cured after the film is used for the test). Membrane rate (%) = (final film thickness dm without imaging step) + full exposure film thickness (//m)) x 1〇〇 1260329 _room number 89121019____L· VI. Patent application scope The reference residual film rate is measured. When the calculated residual film rate is equal to the reference residual film rate by the error range of 1% and the minimum exposure amount is determined as the minimum exposure amount, the minimum exposure is I 1 0 0 m J / c m2 or less. a color filter having a coloring layer that is transparent to the transparent substrate and a protective film covering the colored layer; and characterized in that: at least one of the colored layer and the protective film It is formed by hardening the curable resin composition of the above-mentioned patent application.巳 28. A color filter having a transparent substrate, a colored layer formed on the transparent color, and a spacer disposed at a position overlapping the non-display portion to maintain a space between the electrode substrates; wherein: The upper partition is made of the hard spacer of item 25 of the above-mentioned patent application. K &lt; fork 1 匕 tree tree day composition hardened 2 9 · A liquid crystal panel, 2 7 color filters and electrodes. The packaging is particularly advantageous in that the above-mentioned patent application scope is opposed to the liquid crystal compound 30. A liquid crystal panel is characterized in that the color filter of 28 items is paired with the electrode substrate ''. °, encapsulating liquid crystal compounds between the first two of the above patent applications